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# E

MARINE ENVIRONMENT PROTECTION

COMMITTEE

61st session Agenda item 2 MEPC 61/2/10

29 March 2010 Original: ENGLISH

HARMFUL AQUATIC ORGANISMS IN BALLAST WATER

Application for Final Approval of the Special Pipe Hybrid Ballast Water Management System combined with PERACLEAN Æ Ocean (SPO-SYSTEM)

Submitted by Japan

SUMMARY

Executive summary: This document contains the non-confidential information related to the application for Final Approval of the Special Pipe Hybrid Ballast Water Management System combined with PERACLEAN Æ Ocean (SPO-SYSTEM) under 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: 7.1.2.5

Action to be taken: Paragraph 4

Related document: BWM/CONF/36; MEPC 53/24/Add.1, MEPC 53/2/12; MEPC 54/2/12; MEPC 57/2/5, MEPC 57/2/10 and BWM.2/Circ.13

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 Convention shall be approved by the Organization.

2 Japan herewith submits an application for Final Approval according to the "Procedure for approval of ballast water management systems that make use of Active Substances (G9)". This Procedure stipulates the required information (MEPC 57/21, annex 1, paragraph 4.2.1), which, according to section 6, should be evaluated by the Organization. In accordance with BWM.2/Circ.13, the document in the annex contains the non-confidential part of the manufacturer's application dossier, which includes the following:

.1 summary of the application dossier of the Special Pipe Hybrid Ballast Water Management System combined with PERACLEAN Æ Ocean (SPO-SYSTEM) according to Procedure (G9);MEPC 61/2/10 Page 2

I:\MEPC\61\2-10.doc .2 list of references; and

.3 statement of quality control of each test.

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

3 The receiving competent authority in Japan has verified the application dossier and believes it to satisfy the data requirements of Procedure (G9) adopted by resolution MEPC.169(57).

Action requested of the Committee

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

***MEPC 61/2/10 Annex, page 1

I:\MEPC\61\2-10.doc ANNEX

NON-CONFIDENTAL INFORMATION ON THE SPECIAL PIPE HYBRID

BALLAST WATER MANAGEM ENT SYSTEM COMBINED

WITH PERACLEAN Æ OCEAN (SPO-SYSTEM)

This annex has the following content:

1 INTRODUCTION

2 APPLICATION DATA SET

3 USE OF THE ACTIVE SUBSTANCE OR THE PREPARATION

4 MATERIAL SAFETY DATA SHEETS

5 RISK CHARACTERIZATION

6 RISK ASSESSMENT

7 CONCLUSION

8 REFERENCES

LIST OF APPENDICES:

APPENDIX 1 STATEMENT

APPENDIX 2 QUALITY ASSURANCE STATEMENT

APPENDIX 3 QUALITY ASSURANCE PROJECT PLAN (QAPP) FOR

CORROSION TESTING OF SPO-SYSTEM

APPENDIX 4 QUALITY MANAGEMENT PLAN (QMP) AND QUALITY ASSURANCE PROJECT PLAN (QAPP) FOR ANALYSIS OF

BALLAST WATER TREATED BY SPO-SYSTEM

1 INTRODUCTION

1.1 Application process under Procedure (G9) for "Special Pipe Hybrid Ballast Water Management System Combined with PERACLEAN Æ Ocean" (SPO-SYSTEM)

"Special Pipe Hybrid Ballast Water M anagement System Combined with PERACLEAN Æ Ocean" (hereafter referred as SPO-SYSTEM) represents one version of SP-Hybrid BWMS, which uses PERACLEAN Ocean as a Preparation and Peracetic acid (PAA) as well as Hydrogen peroxide (H 2 O 2 ) as Active Substances.

PERACLEAN Æ Ocean to be used for SPO-SYSTEM as a Preparation was reviewed at the first meeting of the GESAMP-BWWG held from 23 to 27 January 2006 and was granted Basic Approval at MEPC 54 in March, 2006. The SEDNA Æ System which uses

PERACLEAN Æ Ocean for BWMS was reviewed at the fifth meeting of the GESAMP-BWWG from 14 to 18 January, 2008 and was granted Final Approval at MEPC 57 from March 31 to April 4, 2008.

The use of PERACLEAN Æ Ocean for the SPO-SYSTEM was approved by Evonik Degussa who had applied for Basic Approval.

The SPO-SYSTEM uses the same PERACLEAN Æ Ocean as the Preparation, which had been granted Basic Approval and its injection concentration is lower than the Basic Approval.MEPC 61/2/10 Annex, page 2

I:\MEPC\61\2-10.doc Also its holding time is the same. Furthermore, the PAA concentration meter is installed so as to survey whether the PAA of the Active Substance goes under the detection limit at time of the ballast water discharge.

1.2 Comments relevant to the PERACLEAN Æ Ocean at the time of Basic Approval (MEPC 54/2/12, annex 5, section 9 "Conclusion and Recommendations")

The following comments were made by the GESA MP-BWWG at time of the Basic Approval. This Final Approval application for the SPO-SYSTEM has been developed taking into

consideration these comments as follows:

.1 Upon application of PERACLEAN Æ Ocean in ballast water, the PAA is degraded almost completely after less than 24 hours. Hydrogen peroxide, however, degrades more slowly with the degradation rate depending on the content of organic matter and particles in the ballast water.

Applying the recommended dosing of 150 mg/L PERACLEAN Æ Ocean, a typical concentration of hydrogen peroxide at 2 mg/L may be expected in the discharged ballast water. In cases where ballast water has a low content of organic matter and particles, and where the holding time is short (48 hours or less), concentrations of up to 15 mg/L of hydrogen peroxide may be expected.

.2 Aquatic toxicity testing with treated ballast water shows that the acute toxicity encountered can be ascribed mainly to the content of hydrogen peroxide. It is further noted that even with the lowest concentration of hydrogen peroxide in the treated ballast water (2 mg/L), a dilution of the discharged ballast water of at least 200 times is required to reach

environmental concentrations below the Predicted No-Effect-Concentration at 10 μg/L according to the EU Risk Assessment Report available.

.3 Exposure modelling has been performed using the MAMPEC model. The assumptions on the scenarios as well as input parameters of the model are not presented in detail, which hinders the evaluation of the reliability of the model results. It appears from the dossier that resulting concentrations in the aquatic environment after discharge and dilution are at the maximum of 5-10 μg/L of hydrogen peroxide which is lower than or equal to the PNEC value established. Thus, the application and discharge of PERACLEAN Æ
Ocean seem to cause no unacceptable harm to the environment.

.4 A number of concerns in relation to safety of ships have been raised in section 5 due to the physico-chemical hazards of PERACLEAN Æ Ocean. These concerns need to be addressed prior to initiation of full-scale testing on board ships.

.5 Based on the submitted scientific information about the toxicological profile of PAA 15% preparation, we can anticipate major concerns towards acute adverse effects (corrosiveness, severe irritant for skin and eye, irritant for the respiratory tract). In this sense, we recommend as mandatory the application of RMM (risk management measures) for the protection of the exposed populations to the main routes of concern: dermal and inhalation. These control measures (PPE and RPE) must be put in place for use and handling of the preparation at the different stages of the process and with the different concentrations applied.MEPC 61/2/10 Annex, page 3

I:\MEPC\61\2-10.doc .6 Additionally, it is recommended that dermal and inhalation sub-chronic effects in presented studies should be further investigated, taking into account realistic occupational exposure scenarios and covering

non-accident situations. These data should be submitted before final approval.

.7 There seems to be insufficient information on degradation of components of

PERACLEAN Æ Ocean during treatment of ballast water as it seems to depend on the content of organics and particles in ballast water. This

should be further studied and reliable estimates or measurements of concentrations of the components at discharge should form the basis for

the environmental risk assessment.

.8 The selection of appropriate scenarios for discharge of treated ballast water needs consideration and justification. This would include proposals for numbers of ships in the harbour, the volume of treated ballast water, the frequency and duration of discharges, the dimensions of the harbour including water volume and flow. The Group notes that this is not necessarily an obligation of the individual applicant, but that this might be considered at a general level (refer to the report of first meeting of the GESAMP-BWWG contained in document MEPC 54/2/12).

1.3 Composition of application for Final Approval

This application addresses the comments made by the GESAMP-BWWG at the time of Basic Approval as outlined in the aforementioned paragraph 1.2. However, as this BWMS has not been installed on board a ship, data on the responses from shipboard tests are not included. This document has been developed by adding further safety information on handling PERACLEAN Æ Ocean on the hypothesis of installation on board a ship and information about acute and chronic toxicity te sts on three kinds of marine organisms by using two kinds of test water with a full-scale land-based test facility, degradation tests of

Active Substances and corrosion tests.

1.4 Application conditions of the system

The following is the application condition of this BWMS:

.1 the injection concentration of PERACLEAN Æ Ocean is 80 mg/L; and

.2 the holding time is at least 24 hours.

1.5 Conclusion of Final Assessment Report

This BWMS uses PERACLEAN Æ Ocean with an injection concentration of 80 mg/L as a Preparation. This injection concentration is almost half of 150 mg/L used for the Basic Approval (see document MEPC 53/2/12). PAA as an Active Substance is added under surveillance by a PAA concentration meter so as not to exceed the detection limit when discharged.

With reference to the use of PERACLEAN Æ Ocean, the result of various tests implemented in a full-scale land-based test facility as well as the risk assessment on the environment, human beings and ships showed that the risks against them were within acceptable ranges. From this point of view, this BWMS deserves the Final Approval.MEPC 61/2/10 Annex, page 4

I:\MEPC\61\2-10.doc 2 APPLICATION DATA SET

2.1 Identification of the Substance or Preparation (G9: 4.1)

2.1.1 Preparations (G9: 4.2.2)

The chemical Preparation used in this BWMS is a specific formulation, made by Evonik Degussa, known as PERACLEAN Æ Ocean, and has been granted Basic Approval. In this BWMS, PERACLEAN Æ Ocean is used at an injection concentration of 80 mg/L. The composition of PERACLEAN Æ Ocean is shown in Table 2.1-1.

Table 2.1-1: Composition of PERACLEAN Æ Ocean

Trade Name of Preparation PERACLEAN Æ Ocean

Composition of Preparation

Component Chemical Name CAS Number Concentration (%) AS, RC or Other *

Peracetic acid 79-21-0 14 ñ < 17 AS

Hydrogen peroxide 7722-84-1 13 ñ < 15 AS

Acetic acid 64-19-7 24 ñ < 29 Other (stabilizer, solvent)

Acidic (e.g., phosphoric acid)

― < 1 Other (stabilizer)

Water 7732-18-5 < 39 ñ 49 Other (solvent)

* Indicate whether the chemical is be lieved to be one of the following, givi ng justification for each proposal: AS = Active Substance; RC = Relevant Chemical ; Other = Any other Chemical, e.g., solvent.

2.1.2 Active Substances

The Active Substances are, specifically, perac etic acid (hereinafter, referred to PAA) and hydrogen peroxide (hereinafter, referred to H 2 O 2 ).

PAA is produced by reacting H 2 O 2 with acetic acid in an aqueous solution. In this process, PAA is not produced as a pure substance, but is produced in the form of an aqueous equibrium solution containing PAA, acetic acid, H 2 O 2 , and water:

CH 3 COOH + H 2 O 2 ↔ CH 3 CO(O 2 )H + H 2 O

As shown in the above equation, an aqueous solution containing PAA has the same

formulation of PERACLEAN Æ Ocean, a Preparation used in this BWMS. Thus PAA and

PERACLEAN Æ Ocean are handled as the same substance on information of toxicity, etc., as described in section 2.2 this document and the followings.

The amount of PAA in the equilibrium solution can range from 0.25 to 40%, depending on the targeted use. This equilibrium solution is a biocidal marketed product. PAA is a biocidal Active Substance with strong bactericidal , fungicidal, and virucidal activities.

H 2 O 2 is commonly viewed as an "environmentally friendly" or "green" chemical. This is particularly due to the physicochemical properties of this inorganic water-soluble substance.

H 2 O 2 is non-persistent, innocuous or even beneficial, can be broken down to produce oxygen, and does not accumulate.MEPC 61/2/10 Annex, page 5

I:\MEPC\61\2-10.doc H 2 O 2 is produced naturally by many living organisms, either within the organism itself or in the surrounding environment. For example, blue-green algae produce H 2 O 2 under light

irradiation at a rate of 1-50 μ g/l per hour (Zepp et al. , 1987).

2.1.3 Relevant Chemicals (G9: 2.1.4)

According to document MEPC 53/2/12, findings concerning the sterilization of river water by PAA suggest that there are no substances corre sponding to the Relevant Chemicals. In regard to the application for the Final Approval of other systems using the same Preparation, however, the GESAMP-BWWG, indi cates in document MEPC 57/2/10, annex 7, paragraph 7.1.4 that a small quantity of trihalomethanes are produced under a low organic load. Also in this BWMS, there was a possibility that by-products may be produced. Thus, the tests listed in section 5.2.2 in this application were conducted.

As a result, small quantities of trihalomethanes, such as bromodichloromethane, dibromochloromethane, and bromoform were produced by ballast water treatment with this BWMS. Therefore, these three compounds are considered as Relevant Chemicals. The production of bromodichloromethane was confirmed only in some tests, and after 5 days, it reached below the detection limit. However, it is presumed that its decay results volatilization into the atmosphere. Due to its non-degradable properties, in this application,

risk assessment was conducted on it as in other trihalomethanes.

The following mechanism was considered regarding the production of trihalomethanes:

Figure 2.1-1: Reactions of Hydrogen Peroxide (H 2 O 2 ), Peracetic Acid (PAA)

and Bromide Ion in water

Table 2.1-2 provides information on the Relevant Chemicals and the maximum detection concentrations, etc., found during the treatment by this BWMS. H + H 2 O 2 HOBr Natural Organic

Matter (NOM) Bromoform

Bromodichloromethane

Dibromochloromethane

H 2 O 2 H 2 O 2 (HO 2 - )

Acetic acid PAA

Br - BrO -MEPC 61/2/10 Annex, page 6

I:\MEPC\61\2-10.doc Table 2.1-2: List of ALL potential by-products in ballast water

Chemical Name CAS Number Concentration (mg/L)

in treated ballast water (bio)degradation rate or

half-life

Bromoform 75-25-2 14.5 μ g/L Non-degradable

Bromodichloromethane 75-27-4 0.31 μ g/L In the test, ND after 48 hours

Dibromochloromethane 124-48-1 1.75 μ g/L Non-degradable

2.1.4 Other Chemicals

Preparation PERACLEAN Æ Ocean contains acetic acid, acid and water as a stabilizer or solvent (see Table 2.1-1). This corresponds to Other Chemicals

.

However, acetic acid, its salts and acetate naturally occur in the environment and living organisms. Furthermore they are rapidly biodegraded. Due to their scientific characteristics,

PERACLEAN Æ Ocean preparations are not the object of risk assessment. In addition, this classification is also applicable to other systems using PERACLEAN Æ Ocean, which was granted Final Approval. See below:

Acetic acid: Stabilizer, solvent

Acid: Stabilizer

Water: Solvent

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

2.2.1 Acute aquatic toxicity

2.2.1.1 Acute aquatic toxicity of PERACLEAN Æ Ocean and PAA

Available data on the acute toxicity of PERACLEAN Æ Ocean on seawater and fresh water organisms was presented in the application for Basic Approval for PERACLEAN Æ Ocean (MEPC 53/2/12) and the application for Final Approval (MEPC 57/2/5) for other system using the same Preparation. This data is summarized below:

.1 The results of the toxicity tests for different fresh water species show differences in sensitivity ñ sma ll organisms are more sensitive to

PERACLEAN Æ Ocean than large ones. The Active Substance, PAA, is well known for its bactericidal effect, and this ranking is not surprising. Comparing the results concerning daphnia, fish, and algae with recent findings (ECETOC-JACC 2001), the values correspond favourably.

.2 The acute toxicity of PERACLEAN Æ Ocean was investigated in two marine algae species, Macroystis pyrifera and Skeletonema costatum . The EC 50 values (48 hours) in Macroystis pyrifera were 7.91 mg PERACLEAN Æ
Ocean/L for germination and 10.9 mg PERACLEAN Æ Ocean/L for germ tube length, corresponding to 1.19 and 1.64 mg PAA/L, respectively. The species Skeletonema costatum , exposed for 96 hours, was found less sensitive, with an EC 50 value of > 16 mg PERACLEAN Æ Ocean/L, corresponding to 2.4 mg PAA/L (MEPC 57/2/5).MEPC 61/2/10 Annex, page 7

I:\MEPC\61\2-10.doc .3 In an additional acute toxicity test with PERACLEAN Æ Ocean (test duration: 96 hours, water renewal after 48 hours), using the pacific herring ( Clupea pallasi ), no toxic effects were observed up to the highest test concentration of 16 mg PERACLEAN Æ Ocean/L. Therefore, the

LC 50 became > 16 mg PERACLEAN Æ Ocean/L, which corresponds to >2.4 mg PAA/L (MEPC 57/2/5).

.4 Comparing available results obtained for the three trophic levels (not restricted to PERACLEAN Æ Ocean), fish was found to be less sensitive (lowest acute LC 50 is 0.91 mg PAA/L). For invertebrates, the lowest EC 50 was obtained for Thamnocephalus platyurus , with 0.183 mg PAA/L.

.5 Acute toxicity has relation to the si ze of test organisms.Embryonic stages of oysters and mussels were found to be most sensitive, with 48-hour EC 50 values of 0.27 to 0.54 mg PAA/L.

.6 Results of acute aquatic toxicity in the application for Final Approval (MEPC 57/2/5) for other system using the same Preparation are in the same range as those of previously presented data in the application for Basic Approval application of PERACLEAN Æ Ocean (MEPC 53/2/12).

2.2.1.2 Acute aquatic toxicity of H 2 O 2

Data on H 2 O 2 toxicity for seawater and fresh water organisms is presented in the application for Basic Approval (MEPC 53/2/12) and the applic ation for Final Approval (MEPC 57/2/5) for other system using the same Preparation.

The minimum acute toxicity value of H 2 O 2 is 72-hour ECr 50 at 1.38 mg/L for Alga,

Skeletonema costatum . Therefore, 1.38 mg/L was used as acute aquatic toxicity data to be

used for different risk assessments of H 2 O 2 in this application.

2.2.1.3 Acute aquatic toxicity of Relevant Chemicals

The acute aquatic toxicity of Relevant Chemicals in this BWMS ñ bromoform, bromodichloromethane, and dibromochloromethane ñ is described below:

.1 The minimum acute toxicity value for seawater species of bromoform is 12 mg/L for fish, Brevoorita tyrannus . Therefore, 12 mg/L was used as acute aquatic toxicity data to be used for different risk assessments of bromoform acute aquatic toxicity to aquatic environment in this application.

.2 The minimum acute toxicity value of bromodichloromethane is 11.6 mg/L for fresh water alga, Psuedokirchneriella subcapitata . Therefore, 11.6 mg/L was used as bromodichloromethane acute aquatic toxicity data to be used

for different risk assessments of the aquatic environment in this application.

.3 The minimum acute toxicity value of dibromochloromethane is 9.6 mg/L for fresh water alga, Psuedokirchneriella subcapitata . Therefore, 9.6 mg/L was used as dibromochloromethane acute aquatic toxicity data to be used for different risk assessments of the aquatic environment in this application.MEPC 61/2/10 Annex, page 8

I:\MEPC\61\2-10.doc 2.2.1.4 Acute aquatic toxicity of the treated ballast water by SPO-SYSTEM

Using a full-scale land-based test facility of SPO-SYSTEM (treatment flow rate: 200 m 3 /h), an acute aquatic toxicity test on treated ballast water was conducted from 1 to 13 October 2008. The simulated ballast water used for exposure in this test was obtained by treating test water under seawater and brackish water criteria prescribed in Guidelines (G8). The injection

concentration of PERACLEAN Æ Ocean was 150 mg/L, almost twice the concentration in the application. Test results are summarized below:

.1 Seawater test

The acute toxicity value based on the above seawater test results

was 72-hour ECr 50 at 13.2%, obtained when Skeletonema costatum (algae) was exposed to the test water (24-hour holding after treatment).The PAA

concentration of 13.2% diluted water was lower than the lower detection limit (<0.5 mg/L), and the H 2 O 2 concentration was 1.0 to 2.8 mg/L. These conformed to the results at the time of the Basic Approval, Final Approval for other system using the same Preparation, and the above mentioned acute aquatic toxicity value.

.2 Brackish water test

The acute toxicity value based on the above results of the brackish test was

the 72-hour ECr 50 at 10.7%, obtained when Skeletonema costatum (algae) was exposed to the test water (after 24-hour holding after treatment). The

PAA concentration of the 10.7% diluted water was lower than the lower detection limit (<0.5 mg/L), and the H 2 O 2 concentration was 1.7 to 2.6 mg/L.

These results are the same level as that of seawater test.

2.2.2 Chronic aquatic toxicity

2.2.2.1 Chronic aquatic toxicity of PERACLEAN Æ Ocean and PAA

Existing data on the chronic toxicity of PERACLEAN Æ Ocean to seawater and fresh water organisms are presented in the application for Basic Approval (MEPC 53/2/12) and the application for Final Approval for other system using the same preparation (MEPC 57/2/5).

This data is summarized below:

.1 A fish early-life stage test with the fresh water fish, Danio rerio , was performed according to OECD 210. Neither the effects on hatching success nor behavioural and morphological changes were observed. The only effect seen was reduced survival in the two highest concentrations (15 and 150 μ g/L PERACLEAN Æ Ocean) in a time range of 5-12 days post hatching. No mortality change, depending on concentration, was observed. Furthermore, the overall NOEC is considered to be 2.25 μ g PAA/L (MEPC 57/2/5).

.2 Based on a specific study protocol (non-GLP) recommended by the Washington State Department of Ecology, a 16-day fish embryo development test using pacific herring ( Culpea pallasi ) gametes with

PERACLEAN Æ Ocean was performed. The NOEC (endpoint: percentage of hatched larvae) was 1.9 mg PERACLEAN Æ Ocean/L (0.29 mg PAA/L) (MEPC 57/2/5).MEPC 61/2/10 Annex, page 9

I:\MEPC\61\2-10.doc .3 The NOEC for Macroystis pyrifera (germination tube length) was 4 mg

PERACLEAN Æ Ocean/L (0.6 mg PAA/L). The species Skeletonema costatum was found less sensitive with a NOEC of 8 mg PERACLEAN Æ Ocean/L (1.2 mg PAA/L) (MEPC 57/2/5).

.4 The results for marine algae indicate that marine algae are less sensitive to

PERACLEAN Æ Ocean than fresh water species (MEPC 53/2/12). All referenced studies indicate a very steep dose response curve. However,

fish larvae were much more sensitive than Daphnia magna (a long-term NOEC of 0.05 mg/L), leading to an overall NOEC of 2.25 μ g PAA/L, based

on the results of the fish test.

.5 Using an assessment factor of 10, a PNEC of 0.225 μ g/L can be derived corresponding to a PNEC of 1.5 μ g PERACLEAN Æ Ocean/L.

2.2.2.2 Chronic aquatic toxicity of H 2 O 2

Data on H 2 O 2 chronic toxicity to seawater and fresh water organisms is presented in the application for Basic Approval (MEPC 53/2/12) and the application for Final Approval for other system using the same preparation (MEPC 57/2/5). The minimum chronic toxicity value of H 2 O 2 is NOEC 0.1 mg/L for fresh water Alga, Chlorella vulgaris

. 

### Therefore, 0.1 mg/L was used as


### chronic aquatic toxicity data to be used for different risk assessments of H 2 O 2 in this application.

2.2.2.3 Chronic aquatic toxicity of Relevant Chemicals

The chronic aquatic toxicity of the Relevant Chemicals for this BWMS ñ bromoform, bromodichloromethane, dibromochloromethane ñ is described below:

.1 The minimum chronic toxicity value of bromoform is MATC (Maximum Acceptable Toxicant Concentration) at 4.8 mg/L for fresh water fish, Cyprinodon variegates. Therefore, a NOEC (MATC) of 4.8 mg/L was used as the bromoform chronic aquatic toxicity data to be used for different risk assessments of aquatic environm ents in this application.

.2 The minimum chronic toxicity value of bromodichloromethane is the 21-day

NOEC at 0.78 mg/L for fresh water fish, Oryzias latipes. Therefore, a

NOEC of 0.78 mg/L was used as the bromodichloromethane chronic aquatic toxicity data to be used for different risk assessments of aquatic environments in this application.

.3 The minimum chronic toxicity value of dibromochloromethane is the 21-day NOEC at 0.063 mg/L for fresh water crustacean, Daphnia magna. Therefore, a NOEC of 0.063 mg/L was used as the dibromochloromethane chronic aquatic toxicity data to be used for different risk assessments of aquatic environments in this application.

2.2.2.4 Chronic aquatic toxicity of treated ballast water by SPO-SYSTEM

Using Guidelines (G8) full-scale land-based test facility of SPO-SYSTEM (treatment flow

rate: 200 m 3 /h), a chronic aquatic toxicity test of treated ballast water was performed from 27 November to 24 December 2008. The ballast water used for exposure was obtained by treating test flow water under the seawater and brackish water criteria prescribed in Guidelines (G8). The injection concentration of PERACLEAN Æ Ocean was 150 mg/L, nearly twice the application-use concentration.MEPC 61/2/10 Annex, page 10

I:\MEPC\61\2-10.doc Test results are summarized below.

.1 Seawater test

The lowest no observed effect concentration based on seawater test was the 72-hour NOEC at <10% and 21-day NOEC at 10%, obtained when

Skeletonema costatum (algae) and Hyale barbicornis (crustacean) were exposed to test water. The PAA concentration of 10% diluted water was lower than the detection lower limit (<0.5 mg/L), and the H 2 O 2 concentration was 1.0 mg/L. These conform to the results at the application of Basic Approval and Final Approval for other system using the same Preparation.

.2 Brackish water test

The no observed effect concentration based on brackish water test was the 72-hour NOEC at 3.2%, obtained when Skeletonema costatum (algae) was exposed to test water. The PAA concentration of the 3.2% diluted water was lower than the detection lower limit (<0.5mg/L), and the H 2 O 2 concentration was 1.3 mg/L. This value is the same level as that of seawater.

2.2.3 Endocrine disruption

I nformation was unavailable for the endocrine disruption of Preparation PERACLEAN Æ Ocean,

Active Substances PAA and H 2 O 2 , and Relevant Chemicals bromoform,

bromodichloromethane and dibromochloromethane.

This is because they are not listed in the EUROPEAN COMMISSION DG ENV, "Towards the establishment of a priority list of substances for further evaluation of their role in endocrine disruption", 2000, and probably because the endocrine disruption of these compounds is not supposed in view of their structure.

2.2.4 Sediment toxicity

Information was unavailable concerning the toxicity effects of Preparation PERACLEAN Æ

Ocean, Active Substances PAA and H 2 O 2 , and the Relevant Chemicals bromoform, bromodichloromethane, and dibromochloromethane on benthic habitants. On the basis of the GESAMP-BWWG Methodology (MEPC 57/2/ 10, annex 4, paragraph 3.2.4), bromoform shows a logPow of 2.4, bromodichloromethane shows a logPow of 2.10, and dibromochloromethane shows a logPow of 2.16. All the values are smaller than a logPow of 3, which causes sediment adsorption and accumulation. Thus, it is not supposed that

these substances show bottom s ediment toxicity (EU-RAR 2003).

2.2.5 Bioavailability/biomagnification/bioconcentration

PAA and H 2 O 2 are highly water-soluble and readily degradable in the environment and organisms; thus, the possibility of biomagnification/bioconcentration is considered low. Concerning biomagnification/bioconcentration of bromoform, data is available on fresh water carp. Here, the BCF is 7.1ñ21 and 7.7ñ19, respectively, with a six-week exposure of bromoform at 0.1 mg/L and 0.01 mg/L. Accordingly, the possibility of biomagnification/ bioconcentration is believed to be low, and the fact that bromoform's logPow value is as

small as 2.4 conforms well to the BCF.MEPC 61/2/10 Annex, page 11

I:\MEPC\61\2-10.doc Concerning biomagnifications/bioconcentration of bromodichloromethane, the BCF in fish is 7. Accordingly, the possibility of biomagnification/bioconcentration is believed to be low, and the fact that bromodichloromethane's logPow value is as small as 2.1 conforms well to the BCF.

Concerning biomagnification/bioconcentration of dibromochloromethane, the BCF in fish is 9. Accordingly, the possibility of biomagnification/bioconcentration is believed to be low, and the fact that dibromochloromethane's logPow is as small as 2.16 conforms well to this BCF.

2.2.6 Food web/population effects

Both PAA and H 2 O 2 are highly water-soluble due to their log Pow values and undergo

immediate in vivo degradation through such enzymes as catalase and peroxidase. Therefore, no bioaccumulation is assumed, and no effect is expected on humans through

such food.

The BCF of bromoform, bromodichloromethane and dibromochloromethane is <21, 7 and 9, respectively, indicating low bioaccumulation in living organisms (algae, invertebrates and fish) constituting the food web. For this reason, effects on the food web/population are unlikely.

2.3 Data on mammalian toxicity (G9: 4.2.1.2)

2.3.1 Acute toxicity

2.3.1.1 Data on mammalian acute toxicity of PERACLEAN Æ Ocean and PAA

In oral administration of PAA to rats, LD 50 was 152 mg/kg bw (MEPC 53/2/12) and 36.7-98.9 mg/kg bw (ECETOC-JACC 2001). Main symptoms included decreased activity, diarrhea, increased secretion from nasal cavities and eyes, piloerection, gasping, excessive urination, ptoses, coloration of the nostrils and the back, salivation, and gasping sounds. These effects disappeared following the end of the 14-day observation (ECETOC-JACC 2001). In dermal administration to rabbits, LD 50 was 229 mg/kg bw (MEPC 53/2/12) and 223.5ñ232.6 mg/kg bw (ECE TOC-JACC 2001), with main symptoms including decreased activity, diarrhea, increased secretion from nasal cavities, piloerection, salivation, and lower gauge rotation. However, no pathological change was observed. Local effects included moderate to severe erythema, slight to severe edema, and crust formation (ECETOC-JACC 2001). In inhalation to rats, LD 50 was 0.51ñ1.26 mg/L/4 h (aerosol), 0.08ñ0.19 mg/L/4 h (vapour) (MEPC 53/2/12), and > 0.24 mg/L/4h (ECETOC-JACC 2001). Main symptoms consisted of irregular breathing and wetted body hair. However, no change was confirmed in necropsy. The acute toxicity of PERACLEAN Æ
Ocean and PAA was observed mainly in local infl ammation of the application site. The toxicity varies depending on the composition and concentration of the solution exposed.

2.3.1.2 Data on mammalian acute toxicity of H 2 O 2

In oral administration of H 2 O 2 to rats, LD 50 was 874 mg/kg bw (male) and 801 mg/kg bw (female). Main symptoms included lethargy, rigidity, irregular breathing, hunched posture, and form change in the tongue, esophagus, and duodenum. In an experiment with dermal administration to rabbits, LD 50 was -700 mg/kg bw, when a 90% solution was used. Main symptoms consisted of lacrimation, secretion from nasal cavities, erythema, edema, skin discoloration, eschar, shedding of epidermis, and reduced body weight. In inhalation to rats,

LD 50 was 1.69-2.36 mg/L/4 h, with main symptoms being agitation, calming, ataxia, shiver, paralyzed extremities, and increased respiration rate (EU-RAR 2003). The acute toxicity

of H 2 O 2 was seen mainly in local inflammation of the application site and in generalized symptoms caused by oxygen gas generated as the result of its decomposition.MEPC 61/2/10 Annex, page 12

I:\MEPC\61\2-10.doc 2.3.1.3 Data on mammalian acute toxicity of Relevant Chemicals

The acute toxicity of bromoform, bromodich loromethane and dibromochloromethane can be

summarized as follows:

.1 In oral administration of bromoform, LD 50 was 933 mg/kg bw (mice) and 707 mg/kg bw (rats) (ATSDR 2005). Among bromine-derived THMs, acute lethal activity is lowest in bromoform. Toxicity symptoms caused by bromoform are said to be associated with impaired renal function (IPCS-EHC 2000). No quantitative information was available. Additionally, skin and eye irritation, headache, dizziness, forgetfulness, exanimation, twitch, and pneumonedema have been reported (U.S. NLM: HSDB 2003).

.2 In accidental ingestion cases, central nervous depression is seen, such as lethargy and areflexia, and even a small dose can cause fatigue, headache, and dizziness (ACGIH 2001a). For oral administration to humans, a case has been reported in which a death was caused at 143 mg/kg of bromoform (U.S. NIOSH 2002).

.3 In oral administration of bromodichloromethane, LD 50 was 450 (male) to 900 (female) mg/kg bw (mice), and 916 (male) to 969 (female) mg/kg bw (rats) (MEPC 57/2/10, IPCS-EHC 2000). In an experiment involving oral administration of bromodichloromethane to rats, impaired hepatic and renal function, ataxia, calming, difficult breathing, and sensory paralysis has been observed (IPCS-EHC 2000).

.4 In oral administration of dibromochloromethane, LD 50 was 848 (female) to 1,186 (male) mg/kg bw (mice), and 800 (male) to 1200 (female) mg/kg bw (rats) (IPCS-EHC 2000, ATSDR 2005). In an experiment involving oral administration of dibromochloromethane to mice, ataxia, calming, and sensory paralysis were reported (IPCS-EHC 2000).

2.3.2 Corrosion/irritation/sensitization

2.3.2.1 Corrosion/irritation/sensitization of PERACLEAN Æ Ocean and PAA

PERACLEAN Æ Ocean is extremely corrosive to the skin and eyes and can cause serious inflammation in the mucosa of the respiratory tract. The RD 50 of aerosol generated from products having similar components was 21.5ñ24.1 mg/m3 (ECETOC-JACC 2001).

Document MEPC 54/2/12 recommended the implementation of a skin infiltration test with PAA. Based on the findings of an experiment on PERACLEAN Æ Ocean for toxicokinetics, repeated dose toxicity and corrosive properties, there was no need to obtain further data in response to the recommendations for risk assessment and appropriate risk control (MEPC 57/2/5).

In a test with percutaneous administration to rabbits of PAA/H 2 O 2 /AcOH mixtures, a 17% PAA solution demonstrated corrosiveness, but a 0.35% PAA solution did not.

In a four-hour test exposure to rabbit eyes involving a 0.15% PAA solution, slight irritation was noted. A 0.2% or more concentration showed an irritant property. A 5% solution caused irreversible impairment (ECETOC-JACC 2001).

In a B ̧hler test on guinea pigs using varying compositions (5% and 12% PAA), no skin irritability was observed (ECETOC-JACC 2001).MEPC 61/2/10 Annex, page 13

I:\MEPC\61\2-10.doc 2.3.2.2 Corrosion/irritation/sensitization of H 2 O 2

In an eye irritation test involving rabbits using the Draize method, irreversible eye irritation
was observed at a 10% H 2 O 2 concentration, moderate irritation at 8%, and slight irritation at 5% (EU-RAR 2003).

An exposure test on mice using 70% H 2 O 2 aerosol demonstrated a 50% reduction in respiratory volume and irritation in the respiratory system at 696 mg/m 3

, as the result of exposure to high-concentration aerosol (EU-RAR 2003).

For sensitization, no test report is available for evaluation. However, given the fact that H 2 O 2 has been used for several decades commercially and by individual consumers, it is extremely unlikely that H 2 O 2 is a highly sensitizing substance (EU-RAR 2003).

2.3.2.3 Corrosion/irritation/sensitization of Relevant Chemicals

The effects on the skin and eyes of bromoform, bromodichloromethane, and

dibromochloromethane can be summarized as follows:

.1 According to a report, bromoform caused moderate irritation in a rabbit's skin after repeated contact (ACGIH, 2001a). Irritation in humans can cause reddening and can be absorbed through the skin (IPCS 2006).

.2 In one report, the application of undiluted bromoform caused moderate eye irritation in rabbits, but the symptom disappeared in 1-2 days (ACGIH 2001). Eye irritation in humans is accompanied by reddening or pain (IPCS-EHC 2000).

.3 Animal study data was not available concerning bromodichloromethane. Because bromoform, belonging to the same halogenated methane group as bromodichloromethane, can cause moderat e irritation, bromodichloromethane is likely to demonstrate a similar level of irritation.

.4 Animal study data was also not available concerning dibromochloromethane. Again, because bromoform, belonging to the same halogenated methane group as dibromochloromethane, causes moderate irritation, dibromochloromethane is likely to demonstrate a similar level of irritation.

2.3.3 Repeated-dose toxicity

2.3.3.1 Repeated-dose toxicity of PERACLEAN Æ Ocean and PAA

In a 90-day oral repeated-dose test on rats with 5% PAA, NOAEL = 5 mg/kg bw/day was obtained by local irritation. This dosage corresponds to 1.7 mg/kg bw/day for 15% PAA (ECETOC-JACC 2001).

In an experiment dermal administering PAA/H 2 O 2 /HOAc = 40/14/27 to guinea pigs at a PAA concentration of 3.84 mg PAA/kg bw/day for 28 days and 90 days, slight skin irritation, reduced body weight gain, slight elevation of liver enzymes and LDH, slightly decrease in liver weights, increased leukocyte count, and relatively increased kidney and spleen weight were observed. However, no histopathological change was confirmed in the liver and kidneys (ECETOC-JACC 2001).MEPC 61/2/10 Annex, page 14

I:\MEPC\61\2-10.doc In an inhalation test of mice to PAA/H 2 O 2 /HOAc = 40/14/27 for 29 days, difficult breathing, eye irritation, reduced body weight gain, increased death rate, increased leukocyte and erythrocyte count, increased hemoglobin count and hematocrit value, and lung inflammation were noted. NOAEC = 281 mg PAA/m 3 (ECETOC-JACC 2001).

Repeated-dose toxicity tests using a diluted PAA aqueous equilibrium solution can apply to

PERACLEAN Æ Ocean. Similarly, tested chemicals must be diluted prior to administration to test animals to levels suitable for repeated doses.

Another repeated toxicity test is not required for PERACLEAN Æ Ocean for the reasons stated

below.

No practicable tests have demonstrated overall the toxicity of an aqueous equilibrium

solution of PAA.

These facts are based on toxicokinetic data (see MEPC 53/2/12, annex 7, section 2.2.1) which confirm that PAA does not spread outside the initial application site. The effects of the application depend on the ability of the chemical to cause acute inflammation (i.e. concentrations) and its ability to release oxygen. The mechanism of action and the no observed effect concentration are not considered to vary depending on the specific difference or the length of test period.

2.3.3.2 Repeated-dose toxicity of H 2 O 2

In a 40- to 100-day test with gavage administration to rats, reduced body weight gain, increased spleen weight, decreased hematocrit and serum protein levels, lower erythrocyte count, and reduced hemoglobin concentration were observed. In this test, NOAEL was 20 mg/kg bw/day (EU-RAR 2003).

In a 90-day test exposing rats to H 2 O 2 in drinking water, a dose-related decrease in food intake and water consumption and mucosal hyperplasia were observed. NOAEL was 26-37 mg/kg bw/day (EU-RAR 2003).

In a 28-day inhalation exposure study on rats, respiratory irritation, epidermal necrosis and inflammation in nasal cavities, mononuclear cell infiltration in the pharynx, and neutrophil infiltration and bleeding in perivascular regions of the lung were noted at 14.6 mg/m 3 or more. NOAEC was 2.9 mg/m 3 (EU-RAR 2003).

2.3.3.3 Repeated-dose toxicity of Relevant Chemicals

The toxicity of bromoform caused by oral administration can be summarized as follows:

.1 In a 14-day experiment with oral administration to ICR mice of 50-250 mg/kg/day of bromoform, the 250 mg/kg/day group demonstrated reduced fibrinogen content of the blood, heightened activity of aspartate aminotransferase (AST), decreased blood glucose levels and blood urea nitrogen (BUN) levels, and lower oral and cellular immune functions (reduced IgM antibody-forming cell count in the spleen and lower delayed allergic reaction) were noticed (ATSDR 2005). According to a screening test report, bromoform does not interfere with the transformation by the mitogen LPS (cell wall lipopolysaccharide) of spleen B cells obtained from C3H/He mice or the transformation by mitogen ConA (Concanavalin A) of spleen T cells obtained from BALB/C mice, and does not affect cellular immunity or humoral immunity (ATSDR 2005).MEPC 61/2/10 Annex, page 15

I:\MEPC\61\2-10.doc .2 In a 14-day experiment with oral administration to ICR mice of 72, 145, and 289 mg/kg/day of bromoform, hepatic focal inflammation, increased mitosis in hepatic cells, hyperplasia of kidney tubular epithelium, and glomus degeneration were observed in the 145 mg/kg/day or more group (ATSDR 2005).

.3 In a 14-day experiment with oral gavage of 0, 50, 100, 200, 400, and 600 mg/kg/day of bromoform to B6C3F1 male mice, and 0, 100, 200, 400, 600, and 800 mg/kg/day to female mice, deaths were noted in the 600 mg/kg/day male group and the 800 mg/kg/day female group. Lethargy and ataxia were observed in the 600 mg/kg/day male group and the 600 mg/kg/day or more female group (NTP 1989).

.4 In a 13-week (five days/nine wee ks) oral gavage to B6C3F1 mice of 0, 25, 50, 100, 200, and 400 mg/kg/day of bromoform, hepatic cell vacuolation was noticed in the 200 mg/kg/day or more group, and reduced body weight gain was observed in the 400 mg/kg/day group (IPCS-EHC 2000).

.5 In a test conducted after a 90-day oral gavage to ICR male mice of 10 mg/kg of bromoform, no effect of the dosage was confirmed. In the 100 and 400 mg/kg dose groups, in which many deaths occurred, a change was observed in part of their operant behaviour (ATSDR 2005).

.6 In a 103-week experiment with oral gavage of 0, 50, and 100 mg/kg/day B6C3F1 of bromoform to male mice and 0, 100, and 200 mg/kg/day of bromoform to female mice, the 100 mg/kg/day or more female group demonstrated fatty degeneration of hepatic cells and the 200 mg/kg/day female group showed hyperplasia of the thyroid follicular epithelium (NTP 1989).

.7 In a 14-day experiment with oral gavage to F344 rats of 0, 50, 100, 200, 400, 600, and 800 mg/kg/day of bromoform, the 400 mg/kg/day or more group expressed reduced body weight gain and thyroid gland enlargement. In the cases involving death, lethargy and ataxia were noted (NTP, 1989).

.8 In a one-month experiment giving bromoform-containing feed to Wistar rats after its microencapsulation to prevent vaporization (males: 0, 680, 2,040, and 6,120 ppm; females: 0, 720, 2,170, and 6,510 ppm), the 680 ppm or more male group displayed slight piloerection and decreased serum glucose. The 720 ppm or more group demonstrated decreased serum cholinesterase activity, lower creatinine levels, and decreased alkaline phosphatase activity in females. In the same group, reduced body weight gain and more frequent histopathological liver vacuolation were noted in both males and females. The 2,170 ppm or more group expressed lower serum glucose levels, declining urea nitrogen levels, and reduced lactate dehydrogenase activity. The same group also showed increased platelet counts in both males and females (2,040 ppm or more in males). The 6,120 ppm group expressed lower triglyceride levels and reduced cholinesterase activity in males. The group also showed increased leukocyte alkaline phosphatase activity on both males and females (6,510 ppm in females). LOAEL was reported at 680 ppm (equivalent to 56.4 mg/kg/day) (ATSDR 2005).MEPC 61/2/10 Annex, page 16

I:\MEPC\61\2-10.doc .9 In a 13-week (five days/nine w eeks) experiment with oral gavage administration to F344 rats of 0, 12, 25, 50, 100, and 200 mg/kg/day of bromoform, the 12 mg/kg/day or more male group demonstrated hepatic cell vacuolation, and the 100 mg/kg/day or more group showed lethargy. A significant difference was observed in the 50 mg/kg/day or more groups. NOAEL was 25 mg/kg/day (NTP 1989).

.10 In a 90-day experiment on SD rats wi th drinking water containing 0, 5, 50, 500, and 2,500 ppm of bromoform and a subsequent, 90-day, non-administration observation period, the 2,500 ppm group demonstrated reduced food intake, reduced weight gain, lower lactase dehydrogenase activity (continuing also during the recovery period), and decreased lymphocyte count (during the recovery period). The 50 ppm or more dose group showed histopathological changes in the liver (vacuolation and fat infiltration) and in the thyroid (decreased follicular size and increased epithelium height). Effects on the liver and the thyroid were also seen with similar frequencies in the control group and the solvent control group. Thus, these effects were not considered to be attributable to the dosages except for the highest dosage group. The changes noted in the highest dosage group were slight and found to be recoverable (ATSDR 2005).

.11 In a 103-week (five days/week) exper iment with oral gavage to F344 rats of 0, 100, and 200 mg/kg/day of bromoform, the 100 mg/kg/day or more group expressed liver inflammation and hepatic cell fatty degeneration (NTP 1989).

.12 In a two-year experiment on Wistar rats with feed containing 0, 400, 1,600, and 6,500 ppm of bromoform after its microencapsulation to prevent vaporization, the 1,600 ppm or more group demonstrated reduced body weight gain, lower triglyceride levels and reduced cholinesterase activity in serum, and pathological changes in the liver, including discoloration, roughening of the liver surface, hepatic cell fatty degeneration, microgranuloma, bile duct overgrowth, a nd biliary fibrosis. No hematological change was confirmed.

.13 In this experiment, bromodichloromethane was also administered. A significant difference in the onset of biliary fibrosis was observed in the group given 6,500 ppm of bromodichloromethane. However, bromoform showed no significant difference (ATSDR 2005). In this application we estimate NOAEL at 400 ppm, but do not adopt it as the data available only exists in a summary.

.14 The following information was obtained concerning the toxicity of bromoform administered by inhalation:

.1 In a 10-day experiment exposing rats to 240 ppm (2,500 mg/m 3 ) of bromoform (total hours unknown) and in a two-month test with 24 ppm (250 mg/m 3 ) administered to rats for four hours/day, both cases expressed impaired prothrombin and glycogen synthesis in the liver and reduced gl omerular rates in the kidneys. This information is from a summary in a report made years ago, and thus it is not reliable (U.S.EPA IRIS 2005).MEPC 61/2/10 Annex, page 17

I:\MEPC\61\2-10.doc .2 For the toxicity of bromoform caused by intravenous administration, the following information is available.

.3 In a 10-day experiment with intravenous administration to guinea pigs of 100ñ200 mg/kg/day, the liver and kidneys showed a pathological change (U.S. NLM: HSDB 2003).

The findings above suggest that bromoform targets repeated-dose toxicity at the liver and kidneys.

.15 In 13-week and two-year studies conducted at NTP using mice and rats,

effects on the liver were observed. These were also confirmed in the control group, and thus, it is impracticable to determine NOAEL accurately. Therefore, based on the effects on the liver (hepatic cell vacuolation) confirmed in a one-month test with oral administration (bromoform-containing feed) to Wistar rats, this application sets LOAEL by oral administration for 680 ppm (56.4 mg/kg/day).

.16 ICSC has suggested that repeated inhalation of bromoform may adversely affect the central nervous system and the liver, causing tissue injury.

.17 As for the repeated-dose toxicity of bromodichloromethane, in a 13-week (five day/week) experiment with oral gavage to rats and mice, dose-related effects were observed, including centrilobular hepatic degeneration in both male and female rats and renal necrosis in the 300 mg/kg bw/day group, renal degeneration and necrosis in male mice in the 100 mg/mg bw/day group, and centrilobular hepatic degeneration in female mice in the 200 mg/kg bw/day or more group. NOAEL was 150 mg/kg bw/day for rats and 50 mg/kg/day for mice (IPCS-EHC 2000).

.18 As for the repeated-dose toxicity of dibromochloromethane, in a 13-week (five day/week) experiment with oral gavage to rats and mice, rats expressed serious injury or necrosis in the liver and kidneys, and vacuolation and degeneration of hepatic cells. Mice showed necrosis, vacuolation, or degeneration of hepatic cells, in addition to tubular degeneration and calcification. Based on these findings, NOAEL was set for 30 mg/kg/day (IPCS-EHC 2000).

2.3.4 Chronic toxicity

2.3.4.1 Chronic toxicity of PERACLEAN Æ Ocean and PAA

No relevant data was available in databases or various literatures.

Document MEPC 54/2/12 recommends chronic inhalation studies on rats. PERACLEAN Æ
Ocean is used in a closed or automated system on board. Access to the system by crew and passengers is restricted, and thus, the skin is rarely exposed to the Preparation (see section 3.2). For this reason, no further chronic inhalation study was considered necessary. This was confirmed in the process of registering PAA as a bactericide (MEPC 57/2/5).

The nature of the toxicological effects (local inflammation and corrosion, and accompanying symptoms) is deducible from the findings of acute and subacute inhalation studies on PAA and subchronic pharynx studies. Currently available data are sufficient to allow effective risk

assessment.MEPC 61/2/10 Annex, page 18

I:\MEPC\61\2-10.doc 2.3.4.2 Chronic toxicity of H 2 O 2

A number of reports are available for chronic toxicity of H 2 O 2 . However, some are poorly designed and others lack important information, and thus, they are not appropriate for evaluation. The data provided in section 2.3.3.2 is sufficient to allow deduction of effects of long-term administration.

2.3.4.3 Chronic toxicity of Relevant Chemicals

As for the chronic toxicity of bromoform, in a 103-week experiment with oral gavage of bromoform (solvent, corn oil) to mice (0, 100, 200 mg/kg bw/day) and rats (0, 50, 100 mg/kg bw/day), female and male rats demonstrated non-neoplastic regions in the liver as fatty degeneration and chronic renal infiltration (IPCS-EHC 2000).

In a one-year experiment with drinking water containing bromoform given to F344 rats (0, 6.2, 29, 57 mg/kg bw/day) and to B6C3F1 mice (0, 8.3, 39, 73 mg/kg bw/day), effects were observed mainly on the kidneys (pathologi cal changes in tubule and renal glomus). This suggests that bromoform affects different organs depending on the solvent or the dose method (IPCS-EHC 2000) used.

As far as we are aware, there are no reports of studies conducted to determine chronic effects of bromoform on humans. Meanwhile, there is a report that trihalomethane in drinking water is associated with a higher incidence of bladder cancer, colon cancer, rectal cancer, and spleen cancer. U.S. NTP judged this report to be incomplete because the experiment did not exclude factors other than trihalomethane (NTP 1989).

As for the chronic toxicity of bromodichloro methane, in a one-year experiment on rats and mice with the administration of bromodichloromethane in drinking water, nephrotoxic effects were observed, such as glomerular injury (IPCS-EHC 2000).

As for the chronic toxicity of dibromoc hloromethane, in a two-year (five day/week) experiment with oral gavage of dibromochlorom ethane to rats and mice; female/male rats in the 40 mg/kg/day or more group demonstrated fatty degeneration in the liver, males in the 40 mg/kg/day or more group and females in the 80 mg/kg/day group showed cytoplasmic degeneration in the liver; and males in the 40 mg/kg/day or more group expressed increased incidents of nephropathy. For mice, cytomegalic cells in the liver, hepatic necrosis, fatty degeneration and calcareous deposition in the liver were observed. Male mice also demonstrated nephropathy (IPCS-EHC 2000).

2.3.5 Developmental and reproductive toxicity

2.3.5.1 Developmental and reproductive toxicity of PERACLEAN Æ Ocean and PAA

The data of the developmental and reproductive toxicity are not reliable, because the testing method is inappropriate and because the endpoints set are irrelevant to the toxicity. For these reasons, it is impracticable to determine the existence of developmental and reproductive toxicity in PAA (ECETOC-JACC 2001).

In a developmental toxicity test based on OECD 414 with administration of a 35% PAA solution in drinking water, no dose-related deformity was observed in foetal mice at the highest testing concentration of 700 mg PAA/L (MEPC 57/2/5).MEPC 61/2/10 Annex, page 19

I:\MEPC\61\2-10.doc 2.3.5.2 Developmental and reproductive toxicity of H 2 O 2

For the developmental and reproductive toxicity of H 2 O 2 , there has been no reliable animal study report in evaluation.

Any reliable standardized testing method (e.g., oral administration by drinking water) would not express any toxicity of H 2 O 2 for the following reasons:

.1 unlike oxygen and water, decomposition products of H 2 O 2 , there is much uncertainty about H 2 O 2 reaching a foetus; and

.2 the mother's local effects are considered to be limited to interfering with the nutritional balance and causing general toxicological effects.

In a 90-day test administering H 2 O 2 in drinking water to catalase-deficient mice, no adverse effects were found on the reproductive system. This suggests that H 2 O 2 is not a reproductive toxicant (EU-RAR 2003).

2.3.5.3 Developmental and reproductive toxicity of Relevant Chemicals

As for developmental toxicity of bromoform, 0, 50, 100, and 200 mg/kg/day oral (gavage) administrations of bromoform were given to pregnant Sprague Dawley rats (15 rats per group) for 10 days from day 6 to day 15 of gestation. In this study, the outer shape, bony framework, and organs of the embryos were observed following the performance of a caesarean section at the end of the pregnancy. No effects of the administrations were observed concerning the weight of the mother rats, embryonic weight, and the pregnant state. Although the tendency of the increase in the incidence of skeletal mutation (mid-parietal bone, delayed sternal ossification, and 14 costae) in the embryos was observed, no increase in visceral abnormality was found. In addition, 50 mg/kg/day was reported as having no effect (ATSDR 2005).

In a 10-day oral (gavage) study using 150, 200 mg/kg/day of bromoform on pregnant F344 rats from day 6 to day 15 of gestation, all embryonic death was found at the dosage where toxity develops in the mother rats (ATSDR 2005).

As for reproductive toxicity of bromoform, test results showed no effect from bromoform on the fecundity of mice (fertility rate, survival rate of infants, weight and gender bias per pair) during the oral (gavage) administration of 50, 100, and 200 mg/kg/day of bromoform to 20 pairs of male and female Swiss CD-1 mice for 105 days. In an oral (gavage) study where 0, 50, 100, and 200 mg/kg/day of bromoform was given to 17 to 20 ICR mice per group, one week prior to mating, during continuous mating for 14 weeks and for three weeks following that (breeding continued until the mating and delivery of F2), in F1, an inhibitation of weight increase in males from the 200 mg/kg/day-treated group, a decrease in kidney weight in males and females, and an increase in liver weight were observed; however, there were no effects on reproductive potential (ATSDR 2005).

No information regarding the developmental and reproductive toxicity of bromoform against

humans was found.

As for developmental toxicity of dibromoc hloromethane, in an oral (gavage) study of pregnant rats from day 6 to the day of gestation, no effect to the number of embryos and foetus body weight was observed. The incidence of anomalies did not increase (IARC 1999c; IPCS-EHC 2000).MEPC 61/2/10 Annex, page 20

I:\MEPC\61\2-10.doc In a 52-week study on BDCM in drinking water at doses of 22 and 39 mg/kg/day, no histrogical changes to the reproductive organs of male rats were observed; however, effects on sperm mobility were found (IARC 1999c; IPCS-EHC 2000).

As for developmental toxicity of dibromochlorom ethane, in an oral (gavage) study in pregnant rats from day 6 to day 15 of gestation, the incidence of anomalies did not increase (IPCS-EHC 2000).

In a two-generation reproductive study of administration to the drinking water of male and female mice, fertility and the gestational index decreased in the 4 mg/L-treated group for the F1 generation, while the gestation index decreased significantly in the F2 generation. In the 1, 4 mg/L-treated groups, the number of F1 and F2 litters and the postnatal four-day survival rate decreased significantly. Other effects were seen, including a decreased lactation index and reduced postnatal body weight. No dominant lethal or teratogenic effects were observed in the F1 or F2 generations (IPCS-EHC 2000).

2.3.6 Carcinogenicity

2.3.6.1 Carcinogenicity of PERACLEAN Æ Ocean and PAA

Following the application of 7,12-dimethylbenz[ a ]anthracene to the ICR Swiss mice, a 0.3, 1, and 3% PAA solution was applied two times/week for 66 weeks, and promoter activity was seen in a dose-dependent manner, but not at 0.3%. However, PAA cannot be classified as an initiator from this test (ECETOC-JACC 2001).

In addition, the mutagenicity/genetoxicity test result was negative, and it can be said that there is no induced carcinogens causing gene mutation (see section 2.3.6.1 of this document).

2.3.6.2 Carcinogenicity of H 2 O 2

In a study of carcinogenicity in mice from administration by drinking water, the formation of dose-dependent tumours to the duodenum was seen, but no carcinogenicity was observed in the rats. In species of mice with hypersensitivity, it was concluded that H 2 O 2 was carcinogenic to the duodenum, although it is at very low level. Tumours disappeared after the discontinuation of the administration (EU-RAR 2003). The carcinogenicity evaluation by the IARC was of Group 3, not classifiable as to its carcinogenicity to humans (IARC 1999a).

2.3.6.3 Carcinogenicity of Relevant Chemicals

An oral (gavage) study was performed in whic h a five days/week oral administration of 0, 50, and 100 mg/kg/day of bromoform was given to B6C3F1 male mice and 0, 100, and 200 mg/kg/day to female mice for 103 weeks. The study results showed that the incidence of tumours did not increase (NTP 1989). In an oral (gavage) study in which 0, 100, and 200 mg/kg/day was given for five days/week to F344 rats for 103 weeks, adenomatous polyposis of the large intestine and adenocarcinoma of the large intestine were observed in male and female rats from the 200 mg/kg/day treated group, and it was reported that the rate of tumour incidence in females is significant if polyposis and adenocarcinoma are included (NTP 1989).

As for intraperitoneal administration, the study of an eight-week observation was performed following the 4, 48, and 100 mg/kg/day intraperitoneal administration 18, 23, or 24 times to male A/St mice, and a significant increase in the number of pulmonary adenoma incidence per rat was observed in the 48 mg/kg/day-treated group; however, no increase was observed in the 100 mg/kg/day treated group (ATSDR 2005).MEPC 61/2/10 Annex, page 21

I:\MEPC\61\2-10.doc As for the initiation, in the study where drinking water containing 500 ppm of phenobarbital was administered for 47 days, following three days after the oral (gavage) administration of 202 mg/kg of bromoform to the partially hepatectomized male SD rats or non-treated rats, it was reported that no nidus of a γ -glutamyl transpeptidase reaction developed in the kidney (ATSDR 2005).

As for the carcinogenicity, as stated above, no increase in the incidence of tumours was observed in the mice in the oral study; howev er, a significant difference was found in the increase of tumour incidence in the large intestine of only the rats at the high dosage of 200 mg/kg/day. In addition, the IARC classified the bromoform to be Group 3 (a substance not classifiable as to its carcinogenicity to humans), due to there being no data regarding human carcinogenicity and the only evidence being limited to that obtained on animals. Meanwhile, the US EPA defined the slope fa ctor of excess risk of carcinogenesis

as 7.9×10 -3 (mg/kg) -1 , based on the study results of female rats (adenomatous polyposis of the large intestine and adenocarcinoma) using the linearized multistage model (LMS) as a carcinogenic substance with no threshold, and the carcinogenicity of bromoform was genotoxic (ATSDR 2005).

The IARC classified bromodichloromethane in Group 2B -possibly carcinogenic to humans (IARC 1999c).

The IARC classified dibromochloromethane in Group 3 ñ not classifiable as to its carcinogenicity to humans (IARC 1999d).

2.3.7 Mutagenicity/genotoxicity

2.3.7.1 Mutagenicity/genotoxicity of PERACLEAN Æ Ocean and PAA

There is no new information concerning PERACLEAN Æ Ocean, PAA, and H 2 O 2 (refer to documents MEPC 53/2/12 and MEPC 57/2/5).

More recent studies of in vitro experiments in mammalian cell cultures, indicate that a PAA solution does not cause significant gen otoxic potential and did not cause gene mutations and chromosomal aberrations in either the presence or absence of a metabolic activation system. Only in one chromosomal aberration assay in vitro a positive result was obtained at highly cytotoxic concentrations (0.3 μ L/mL without S9). However, a recent in

vitro chromosomal aberration assay did not show such an effect, even at cytotoxic concentrations, suggesting that the earlier fi ndings may have been an artifact. PAA did not

induce micronuclei in in vivo mouse micronucleus tests when administered by gavage up to the maximum tolerated dose levels and did not induce unscheduled DNA synthesis in two

recent rats in vivo / ex vivo UDS assays when administered by gavage up to the maximum tolerated dose level. Therefore, it can be concluded that PERACLEAN Æ Ocean and PAA are unlikely to have mutagenic potential or be genotoxic.

2.3.7.2 Mutagenicity/genotoxicity of H 2 O 2

H 2 O 2 was mutagenic and genotoxic in variety of in vitro test systems: the Ames test, in vitro chromosomal aberration, and in the UDS, SCE, and DNA repair tests. On the other hand,

H 2 O 2 was negative in in vivo test systems, including the DNA repair test of an intravenous injection of H 2 O 2 in rat hepatocytes and the micronucleus study of H 2 O 2 administered orally through drinking water and by intraperitoneal injection. On the basis of these results,

H 2 O 2 was shown not to be mutagenic in vivo (EU-RAR 2003).MEPC 61/2/10 Annex, page 22

I:\MEPC\61\2-10.doc 2.3.7.3 Mutagenicity/genotoxicity of Relevant Chemicals

As for mutagenicity of bromoform, in the reverse mutation test (Ames test) performed in a hermetically sealed desiccator using Salmonella typhimurium , a positive reaction was indicated to TA100 and TA1535 without S9 activation (used to investigate the liver extract of rats and metabolic activities) (ATSDR 2005). On the other hand, the ordinary plate method indicated negative. This is due to the loss of bromoform by volatilizing (ATSDR 2005).

In the reverse mutation test (Ames test), which NTP performed by the preincubation method using Salmonella typhimurium , TA 100 without S9 activation, TA97, and TA 98 with S9 activation, a false positive was indicated; however, TA1535 and TA1537 was negative regardless of whether it was with or without S9 activation (NTP 1989).

A positive was indicated in the sex-linked recessive lethal mutation test mating after food containing 3,000 ppm of bromoform was fed to a male Drosophila melanogaster for 3 days. However, it was negative in the same test using intraperitoneal administration (NTP 1989). Meanwhile, a negative was indicated in the gene translocation study performed using oral administration (NTP 1989).

The results were positive in the mutagenic test using mouse lymphoma regardless of whether it was with or without S9 activation (NTP 1989).

As for genotoxicity, a study of Aspergillus nidulans treated with bromoform was performed and an increase in aneuploid expression with S9 activation was found (ATSDR 2005). The results of positive without S9 activation, negative with metabolic activation, and negative for both, were reported in chromosomal aberration tests using Chinese hamster ovarian cells (CHO) (NTP 1989).

On the other hand, a positive result for both was reported in chromosomal aberration tests using Chinese hamster lung cells (CHL) (ATSDR 2005). A negative was shown in the chromosomal aberration test in which bromoform was administered once intraperitoneally to male B6C3F1 mice and a bone marrow smear sample created 24 hours later, but a positive tendency was seen in the micronucleus test (NTP 1989). In addition, negative results were obtained in the micronucleus test in which 0, 175, 350, 700, and 1,400 mg/kg of bromoform were administered once intraperitoneally to male ddY mice and a bone marrow smear sample created 24 hours later (ATSDR 2005). In order to confirm these, another micronucleus test was performed in which 0, 50, 250, and 1,000 mg/kg of bromoform were administered intraperitoneally once to ICR mice and a bone marrow smear sample created 24 and 48 hours later, and the results were negative (ATSDR 2005). In contrast, in the chromosomal aberration tests in which 0, 25.3, and 253 mg/kg of bromoform were administered intraperitoneally once to male and female Long-Evans rats and a bone marrow smear sample created 12 hours later, in the study in which over 25.3 mg/kg and 25.3 mg/kg was administered once each and in which a sample was created 6, 12, 18, and 24 hours later, a positive was shown in the lethal group; 6, 12, and 18 hours later respectively (ATSDR 2005).

Tests for DNA damage were also performed, and bromoform showed a positive result in the SOS chromotest using Escherichia coli , PQ37 (ATSDR 2005). In addition, a positive result was indicated in the Rec-assay using Bacillus subtilis (ATSDR 2005). In the sister chromatid exchange (SCE) test using CHO cells, the results of positive without S9 activation, negative with metabolic activation, and negative with both were reported (NTP 1989). An SCE test in which 200-800 mg/kg of bromoform was administered once intraperitoneally to male B6C3F1 mice and a bone marrow smear sample created 24 hours later was negative; however, a weak positive was observed from the sample created 36 hours later (NTP 1989). In the irregular DNA synthesis (SPS) test of S-phase liver cells in which 0, 200, and 600 mg/kg ofMEPC 61/2/10 Annex, page 23

I:\MEPC\61\2-10.doc bromoform was administered once orally to male B6C3F1 mice and cells collected after killing 48 hours later, the 600 mg/kg-treated group indicated positive (ATSDR 2005). In the unscheduled DNA synthesis (UDS) test of liver cells in which 0, 324, and 1080 mg/kg of bromoform was administered once orally to male SD rats and cells collected after killing two and 14 hours later, the results were negative (ATSDR 2005). No binding was found in the experiment that investigated the binding of liver cells to DNA 16 to 18 hours later following a single oral administration of 14 C-bromoform (2.7 mCi/mmol) to SD rats (ATSDR 2005).

As above, in in vitro tests, opposing results of positive and negative were seen for genotoxicity in the DNA damage test and chromosomal aberration tests using CHL cells or CHO cells. In addition, a positive was shown in the DNA damage and mutagenic test using bacteria and in the chromosomal aberration tests using fungi and the gene mutation test using mouse lymphoma. Moreover, the result s obtained from the SCE test and micronucleus test using mice in in vivo studies show that bromoform is genotoxic.

In addition, no study information was found regarding the mutagenicity/genotoxicity of

bromoform in humans.

The results of in vitro studies for bromodichloromethane are both positive and negative ñ positive and negative in the Ames and chromosomal aberration tests using CHO cells, positive in a mutagenicity test using mouse lymphoma cells with metabolic activation, and negative in that without metabolic activation (IARC 1999c).

The results of in vivo studies showed that sister chromatid exchange was induced in the mouse bone marrow in an oral study, while chromosomal aberration was induced in the rat bone marrow in an intraperitoneal study. However, no micronucleus was induced in the mouse bone marrow in an intraperitoneal study, unscheduled DNA synthesis was not induced in rat livers in an oral study, and DNA strand breakage was not induced in rat kidneys (IARC 1999c).

The results of in vitro studies were both positive and negative in Ames tests; however, they were positive in a test considering the volatility of dibromochloromethane in a closed system. In other studies, positive results were observed in a mutation test using mouse lymphoma cells, a chromosomal aberration test using cells from Chinese hamster lungs (CHL), and a sister chromatid exchange test using human lymphoid cells. In addition, DNA strands were broken in human lymphoblastic leukemia cells, but not in rat primary-cultured hepatocytes (ATSDR 2005).

The results of in vivo studies showed that sister chromatid exchange was induced in the mouse bone marrow in an oral study and chromosomal aberration was induced in the rat bone marrow in oral and intraperitoneal studies. Meanwhile, on the other hand; no micronucleus was induced in the mouse bone marrow in an intraperitoneal study, irregular DNA synthesis was not induced in rat liver in an oral study, and DNA strand breakage was not induced in rat liver, kidneys, and in the duodenum (ATSDR 2005).

2.3.8 Toxicokinetics

2.3.8.1 Toxicokinetics of PERACLEAN Æ Ocean, PAA, and H 2 O 2

Although transdermal and transmucosal absorption is possible for the components of

PERACLEAN Æ Ocean, PAA and H 2 O 2 , they have a small molecular weight, are a highly soluble and low fat soluble substance, and their absorption is limited by their rapid degradation on the entry sites. Systemic absorption is limit ed by their rapid enzymatic degradation in cells of mucous membranes in the skin or digestive organs and respiratory system. For example, contact with severely irritant concentrations of PAA can lead to absorption into the circulatoryMEPC 61/2/10 Annex, page 24

I:\MEPC\61\2-10.doc system due to damaged skin and destruction of the barrier. PAA and H 2 O 2 degrade extremely rapidly in blood, yielding oxygen and acetic acid or oxygen and water, respectively. The remaining acetic acid is a physiological substance absorbed into physiological metabolic pathways or excreted via urine. It is therefore unlikely that organs beyond the site of first contact will be affected (ECETOC-JACC 2001, EU-RAR 2003).

2.3.8.2 Toxicokinetics of Relevant Chemicals

Bromoform administered orally by gavage to ra ts is rapidly absorbed and distributed to the liver, brain, kidney, and adipose tissue. Unchanged bromoform accounted for 67% of the

dose and CO 2 for 4%, and both were excreted through breathing within 8 hours following the administration. Only 4% appeared in urine and 2% was retained in tissues. In contrast, in mice, unchanged bromoform accounted for 6% of the dose and CO 2 for approximately 40%, and both were excreted through breathing within 8 hours following the administration. Five per cent of the dose was excreted in urine, and 8% was retained in tissues (IARC 1999a).

Meanwhile, trihalomethanes including brom odichloromethane and dibromochloromethane are normally thought to be rapidly absorbed and excreted after being metabolized, mainly to CO 2

.

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

2.4.1 Modes of degradation (biotic; abiotic)

2.4.1.1 Modes of degradation of PERACLEAN Æ Ocean, PAA and H 2 O 2

These are investigated in detail in the application for Final Approval for another system that uses the same Preparation (MEPC 57/2/5); and contents of investigation are as follows:

.1 PERACLEAN Æ Ocean is readily biodegradable under conditions according to OECD guidelines. PAA showed rapid degradation, especially in salt water and in the presence of sediment and light. H 2 O 2 degraded slower, but degradation increased significantly in the presence of sediment and salt water.

.2 In fresh water, both components are more stable, especially under cold conditions, and H 2 O 2 was detected over the longer period than that of PAA. Additionally, the presence of sediments facilitates degradation in fresh water.

.3 Under realistic conditions, it can be assumed that sediment, which is usually present in ship ballast water tanks, enhances degradation. When the ballast water is discharged, photolytic degradation additionally occurs. Therefore, the actual environmental concentrations are most probably lower than those measured under laboratory conditions.

2.4.1.2 Modes of degradation of Relevant Chemicals

It can be presumed that bromoform is resistant to biodegradation under aerobic conditions. Meanwhile, the chemical bonds in bromoform are not subject to hydrolysis and do not hydrolyze in a water environment.

Biodegradation of Bromodichloromethane only occurs under anaerobic conditions, and no biodegradation occurs under aerobic conditions. Its speed is relatively fast in that more than 50% biodegrade in half a month to one month (US NLM: HSDB). Hydrolysis does not occur. Biodegradation of Dibromochloromethane only occurs under anaerobic conditionsMEPC 61/2/10 Annex, page 25

I:\MEPC\61\2-10.doc and no biodegradation occurs under aerobic conditions. Its rate is relatively fast in that more than 20% biodegrade in half a month to one month (US NLM: HSDB). Hydrolysis does not

occur.

2.4.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient

2.4.2.1 Bioaccumulation, partition coefficient, octanol/water partition coefficient of

PERACLEAN Æ Ocean, PAA and H 2 O 2

The organic carbon normalized distribution coefficient can be derived from the octanol-water partition coefficients of the Active Substances PAA and H 2 O 2 , using the following equations, according to the EU technical guidance document on risk assessment (EC 2003):

.1 For organic acids, the following equation can be used:

logKoc = 0.6 logKow + 0.32

The log Koc of 0.164 (Koc = 1.45 L/kg) can be calculated for PAA, in which the log Kow is -0.26 at pH 7.

.2 For H 2 O 2 , the following equation for non-hydrophobics can be used:

Log Koc = 0.52 log Kow + 1.02

The log Koc of 0.2 (Koc = 1.58 L/kg) can be calculated for H 2 O 2 using the above equation (EU 2003).

Both Koc values indicate a negligible absorption to organic matter, which would also indicate a very low absorption potential to soil and sediment. This is confirmed by the Mackay level equilibrium distribution (refer to MEPC 53/2/12).

Therefore, the bioaccumulative potential of PERACLEAN Æ Ocean is also presumed to be negligible.

2.4.2.2 Bioaccumulation, Partition Coefficient, and Octanol/Water Partition Coefficient

of Relevant Chemicals

For bromoform, BCF is a maximum of 21 in the study on carp (NITE 2007), and it can be concluded that no bioaccumulation exists. In addition, the logPow value of bromoform is small; 2.4 dovetails with the results.

The maximum logPow value of bromodichloromethane is equivalent to bromoform or lower than 2.1, and it can be concluded that no bioaccumulation exists.

The BCF of dibromochloromethane is 9 and the logP ow value is 2.24. Therefore, it can be

concluded that this substance also is not bioaccumulative.

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

PERACLEAN Æ Ocean contains PAA and H 2 O 2 as Active Substances, as stated in section 2.1.1 in this document. However, as stated in section 2.1.2, these Active Substances degrade into acetic acid and water or into oxygen in a short time. Therefore, persistence is

not assumed in PERACLEAN Æ Ocean, PAA, and H 2 O 2

.MEPC 61/2/10 Annex, page 26

I:\MEPC\61\2-10.doc In contrast, since the produced bromoform, if treated by this BWMS, did not degrade during the test period (5 days after treatment), its half-life was not defined and showed high persistence. However, it is guessed that persistence is not high because bromoform diffuses

in the air for volatile.

2.4.4 Reaction with organic matter

Documents MEPC 53/2/12 and MEPC 57/2/5 state the following:

.1 In addition to the presented studies of disinfectant by-products of PAA in water treatment, the study of effluents and surface water from municipal wastewater treatment plants has been published (Nurizzo et al ., 2005). According to this, a slight amount of aldehydes was detected only under extremely high bromide content (0.9 mg/L) and a high content of oxidizable organic carbon (3.2-4.9 mg/L). No formation of halogenated by-products was observed under any condition.

.2 Additional laboratory findings indicate that no brominated and chlorinated phenols will form during waste water disinfection with PAA.

.3 However, PAA is used as an oxidizing reagent in chemical synthesis (ECETOC-JACC 2001). Additionally, H 2 O 2 is also widely used as an oxidizing reagent and is renowned for oxidation of amine and aldehyde, forming reactions of organic peroxides and expoxides, and it reacts with a wide range of functional groups (EU-RAR 2003).

.4 In addition, as indicated in section 2.1.3 in this document, PAA oxidizes chloride ion and bromide ion in seawater and produces hypochlorous acid and hypobromous acid; these react with natural organic matter and subsequently afford trihalomethanes, as already described.

.5 Furthermore, an increase of AOX was observed as a result of the analysis of the ballast water before and after the treatment using the full-scale land-based test facility. However, it can be said that the reason for this is the addition of a high-concentration of organic matter, in order to fulfil water quality criteria of the Guidelines (G8) land-based test.

.6 Three kinds of THMs are treated as the Relevant Chemicals produced by hypobromous acid, which is THMs precursor and an intermediate product reacting with organic matter (refer to section 2.1.3 in this document). The THMs do not react with organic matter, with the exception of a strong base or powerful oxidants, as they are structurally stable.

2.4.5 Potential physical effects on wildlife and benthic habitats

PERACLEAN Æ Ocean and the Active Substances, PAA and H 2 O 2 , readily degrade in the environment and do not accumulate, as described in detail so far. Additionally, their diffusion in the air is minute, as they are not particularly volatile. Furthermore, as almost all organisms have the enzyme system to eliminate these per oxides, potential effects on the environmental and benthic organisms are low.

The solubility of bromoform in water is 0.1 g/100 mL, and it is dissolved in water at the current discharge concentration of 14.5 μ g/L (refer to section 5.2.2.4 in this document). Therefore it was concluded that potential physical effects are low. On the other hand, someMEPC 61/2/10 Annex, page 27

I:\MEPC\61\2-10.doc bromoform diffused during the vapour phase, due to its high volatility, but such diffused concentration is lower than the background concentration in the air. As such, it can be concluded that the potential physical effects are low.

The solubility of bromodichloromethane in water is 4,500 mg/L, and it completely dissolved in water at the current discharge concentration of 0.31 μ g/L. Therefore, it was concluded that potential effects on benthic organisms are low. On the other hand, as this compound is highly volatile, some diffusion in the vapour phase was expected according to the forecast of environmental distribution (18% distribution in the air) obtained by estimation from Mackay Level III model (EPI SUITE v3.2), but such concentration was lower than the background concentration in the air. As such, it can be concluded that its potential effects on environmental organisms are low.

The solubility of dibromochloromethane in water is 2,700 mg/L, and it dissolved completely in water at the current discharge concentration of 1.75 μ g/L. Therefore, it was concluded that potential effects on benthic organisms are low. On the other hand, as this compound is highly volatile, some diffusion during the vapour phase was expected, according to the forecast of environmental distribution (15% distribution in the air) obtained by estimation from Mackay Level III model (EPI SUITE v3.2), but such concentration was lower than background concentration in the air, and as such, it can be concluded that its potential effects on environmental organisms are low.

2.4.6 Potential residues in seafood

PERACLEAN Æ Ocean, PAA and H 2 O 2 do not accumulate in sea products due to their extremely high water solubility.

Bromoform does not accumulate in sea products, as it has high solubility to water and a logPow of 2.4.

Bromodichloromethane does not accumulate in sea products, as it has high solubility to water and a logPow of 2.10.

Dibromochloromethane also does not accumulate in sea products, as it also has high solubility to water and a logPow of 2.16.

2.4.7 Any known interactive in effects

PAA is used as an oxidant in chemical synt hesis (ECETOC-JACC. 2001). Additionally, H 2 O 2 is widely used as an oxidant, is known for it s oxidation of amine and aldehyde, forming a reaction of organic peroxides and expoxides, and reacts with a wide range of functional groups (EU-RAR 2003).

In addition, as indicated in section 2.1.3 in this document, PAA oxidizes chloride ion and bromide ion in seawater and produces hypochl orous acid and hypobromous acid, and these react with natural organic matter and secondarily produce trihalomethanes.

Bromoform is a relatively stable substance and is persistent under aerobic conditions. Meanwhile, biodegradation occurs due to methane bacteria and denitrifying bacteria under

anaerobic conditions.

Bromodichloromethane is a relatively stable compound and is persistent under aerobic conditions. Meanwhile, biodegradation occurs due to methane bacteria.MEPC 61/2/10 Annex, page 28

I:\MEPC\61\2-10.doc Dibromochloromethane is a relatively st able compound and is persintent under aerobic conditions; however, biodegradation occurs due to methane bacteria.

2.5 Physical and chemical properties for the Active Substances and preparations and treated ballast water, if applicable (G9: 4.2.1.4)

Physical and chemical properties of PAA, H 2 O 2 and Relevant Chemical are shown in

Tables 2.5-1 to 2.5-5.

Table 2.5-1: Physical and chemical properties of Active Substance PAA

Property Value Reference/Comments/

Justification for

missing data Melting point (°C) 0
Boiling point (°C) 105 Flammability (flash point for liquids; °C) 40.5

Density (20°C; kg/m 3 ) 1200
Vapour pressure (20°C; Pa) 2600
Vapour density (air = 1) 2.6 IPCS ICSC 1999

Water solubility (temp; effect of pH; mg/l) Miscible US NLM HSDB 2002

pH in solution 2.6
Dissociation constant (pKa) 8.2

Oxidation-reduction potential 1.81 eV IPCS ICSC 1999

Corrosivity to material or equipment Corrosive to most metals, including

aluminium US NLM HSDB 2002

Reactivity to container

material Not compatible with aluminium, carbon steel, some cross-linked

polyethylene and metal alloys containing copper ECETOC-JACC 2001

Auto-ignition temperature (°C) 200

Explosive properties Above 40.5°C explosive vapour/air mixtures may be formed IPCS ICSC 1999

Oxidizing properties Strong oxidizing agent ECETOC-JACC 2001

Surface tension N/A
Viscosity 3.280 cP at 25.6°C (78°F) US NLM HSDB 2002
Thermal stability and identity of breakdown products Decomposition can be initiated by high temperature, liberating large volume of oxygen gas

Other physical or chemical properties Vinegar-like odour Odour threshold: 50 ppb Henry's law constant: 0.22 Pa

· m 3 /mol ECETOC-JACC 2001

N/A: Not available.MEPC 61/2/10 Annex, page 29

I:\MEPC\61\2-10.doc Table 2.5-2: Physical and chemical properties of Active Substance H 2 O 2

Property Value Reference/Comments/

Justification for

missing data Melting point (°C) -0.43
Boiling point (°C) 150-152 (decomposition) Flammability (flash point for liquids; °C) Not flammable

Density (20°C; kg/m 3 ) 1442.5

Vapour pressure (20°C; Pa) 300 EU-RAR 2003

Vapour density (air = 1) 1 IPCS ICSC 2005
Water solubility (temp; effect of pH; mg/l) Miscible EU-RAR 2003

pH in solution 4.6 (35% w/w) US NLM HSDB 2009d

11.62 EU-RAR 2003 Dissociation constant (pKa) 11.75 US NLM HSDB 2009d

Oxidation-reduction potential As an oxidizing agent: 1.763 V (at pH 0) As a reducing agent: -0.66 V (at pH 0) EU-RAR 2003

Corrosivity to material or equipment Attacks many organic substances IPCS ICSC 2005

Reactivity to container

material Contact with most metals, reductants or organic matters cause violent decomposition with exception of passive material (e.g., stainless steel) EU-RAR 2003

Auto-ignition temperature (°C) Not applicable EU-RAR 2003

May decompose violently if traces of impurities are present; decomposed by many organic

solvents IARC 1985

Explosive properties Reacts violently with combustible and reducing material causing fire and explosion hazard EU-RAR 2003

Strong oxidizer US NLM HSDB 2009d

Powerful oxidizer Oxidizing properties UN classification: 5.1 ( ≥ 8% aq. Solution) EU-RAR 2003

Surface tension 80.4 dynes/cm

Viscosity 1.245 cP US NLM HSDB 2009d

Thermal stability and identity of breakdown products Self-decomposition by heat, to produce oxygen and water

Henry's law constant;

7.5 × 10 -4 Pa·m 3 /mol EU-RAR 2003

Other physical or chemical properties Heat of decomposition;

-28.3 × 10 5 J/kg US NLM HSDB 2009dMEPC 61/2/10 Annex, page 30

I:\MEPC\61\2-10.doc Table 2.5-3: Physical and chemical properties of Relevant Chemicals Bromoform

Property Value Reference/Comments/ Justification for missing data Melting point 8oC ATSDR 2005 Boiling point 149-150oC ATSDR 2005 Flammability No ATSDR 2005 Density (20oC; kg/m 3 ) 2899 ATSDR 2005

Vapour pressure (20oC; Pa) 667 Pa (20oC NTP 2008b

Vapour density (air=1) 8.7 NTP 2008b

Water solubility 3190 mg/L (30oC) U.S. EPA 2005

pH in solution N/A Not hydrolyzed Dissociation constant N/A No dissociable group

Oxidationreduction potential N/A No ionization

Corrosivity to material or equipment Yes ATSDR 2005

Reactivity to container

material Yes ATSDR 2005

Auto ignition temperature (oC) N/A Considered non-flammable due to

chemical structure

Explosive Properties Not considered to be an explosion

hazard MSDS (APPENDIX 2.3)

Oxidizing properties N/A MSDS (APPENDIX 2.3)

Surface tension 41.50mN/m (20oC) NTP 2008b

Viscosity 1.8 cP NTP 2008b

Thermal stability and breakdown product May form toxic

fumes of

bromides when

heated to decomposition MSDS (APPENDIX 2.4)

volatile Other physical and chemical properties Evaporation heat:

46.05 kJ/mol ATSDR 2005

N/A: Not Available.MEPC 61/2/10 Annex, page 31

I:\MEPC\61\2-10.doc Table 2.5-4: Physical and chemical properties of Relevant Chemical

Bromodichloromethane

Property Value Reference/Comments/Justification for missing data

-57 IPCS/ICSC 2006 Melting point (°C) -57.1 IARC 1991

90 IPCS/ICSC 2006 Boiling point (°C) 90.1 IARC 1991 Flammability (flash point for liquids; °C) N/A Not supposed, due to a chemical structure

like bromoform Density (20°C; kg/m 3 ) 1.980 ATSDR 1989
Vapour pressure (20°C; Pa) 6600 IPCS/ICSC 2006

Vapour density (air = 1) 5.6 IPCS/ICSC 2006
Water solubility (temp; effect of pH; mg/l) 4500 (20oC; pH: N/A) IPCS/ICSC 2006

pH in solution N/A Not supposed, due to structure

Dissociation constant (pKa) N/A Not supposed, due to structure

Oxidation-reduction potential N/A Hardly undergoes oxidation/reduction reaction in normal state, due to structure Corrosivity to material or equipment N/A May impair resin, like bromoform

resi N/A May impair resin, like bromoform
Auto-ignition temperature (°C) N/A Non-flammable

Explosive properties N/A Explosive properties are not supposed, due

to chemical structure

Oxidizing properties N/A Oxidizing properties are not supposed due

to chemical structure

Surface tension N/A No data in different databases and literature
Viscosity N/A No data in different databases and literature

Thermal stability and identity of breakdown products On contact with

hot surfaces or

flames this

substance decomposes forming toxic and corrosive gases, including hydrogen

chloride and

hydrogen

bromide IPCS/ICSC 2006

Other physical or chemical properties Reacts with strong bases, strong oxidants and magnesium IPCS/ICSC 2006

N/A: Not Available.MEPC 61/2/10 Annex, page 32

I:\MEPC\61\2-10.doc Table 2.5-5: Physical and chemical properties of Relevant Chemicals

Dibromochloromethane

Property Value Reference/Comments/Justification for missing data Melting point (°C) -20 ATSDR 2005

120 ATSDR 2005 Boiling point (°C) 119-120 (748 mmHg) IARC 1991

Flammability (flash point for liquids; °C) N/A Non-flammable; ATSDR 2005

Density (20°C; kg/m 3 ) 2451 ATSDR 2005
Vapour pressure (20°C; Pa) 10,133 ATSDR 2005

Vapour density (air = 1) N/A Specific gravity believed to be higher than air, like other trihalomethanes Water solubility (temp; effect of pH; mg/l) 2700 (20 oC; pH: N/A) ATSDR 2005

pH in solution N/A Not supposed, due to structure
Dissociation constant (pKa) N/A Not supposed, due to structure

Oxidation-reduction potential N/A Hardly undergoes oxidation/reduction reaction in normal state, due to structure Corrosivity to material or equipment N/A May impair resin, like bromoform

Reactivity to container material N/A May impair resin, like bromoform
Auto-ignition temperature (°C) N/A Nonflammable

Explosive properties N/A Explosive properties are not supposed, due

to chemical structure

Oxidizing properties N/A Oxidizing properties are not supposed due

to chemical structure

Surface tension N/A No data in different databases and literature
Viscosity N/A No data in different databases and literature

Thermal stability and identity of breakdown products N/A Like other trihalomethanes, degradation by heating to produce carbon monoxide, carbon dioxide, hydrogen chloride, and hydrogen bromide gas

Other physical or chemical properties N/A Like other trihalomethanes, it is thought to react with strong bases, strong oxidizing agents, and metal magnesium

N/A: Not Available.

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

Table 2.6-1 shows the determination method for Active Substances, PAA and H 2 O 2 , an d analytical methods for Relevant Chemicals. Details are given in th e toxicity tes t of aquatic organisms.MEPC 61/2/10 Annex, page 33

I:\MEPC\61\2-10.doc Table 2.6-1: Analytical methods at environmentally relevant concentration

Active Substances and Relevant Chemical

Substance Method Applicability Sensitivity Reference/Comments/ Justification for missing

data

PAA Photometric

determination (ABTS method) In liquid 0.5 mg/L Pinkernel U et al. , 1997

H 2 O 2 Redox titration

method (Potassium permanganate) In liquid 0.5 mg/L JIS K1463, 2007

Bromoform

Bromodichloromethane

Dibromochloromethane Purge and trap

GC/MS method In liquid 0.0001 mg/L JIS K0125, 1995

3 USE OF THE ACTIVE SUBSTANCE OR THE PREPARATION

3.1 Outline of SPO-SYSTEM

3.1.1 SPO-SYSTEM principle

This BWMS is a ballast water management system combining chemical sterilization by

Active Substance of PERACLEAN Æ Ocean for Preparation for which Evonik Degussa was granted Basic Approval and physical sterilization by the Special Pipe. Figure 3.1-1 shows the principle of this BWMS.

PERACLEAN Æ Ocean is proportionally injected so that a set concentration is obtained depending on ballast water flow rate. PAA and H 2 O 2 sterilize bacteria in ballast water and then are promptly decomposed in water. The Special Pipe sterilizes aquatic organisms by combination of shearing force generated upstream of the forward slit plate and impact force generated when cavitation formed at the forward slit plate hits the after slit plate and collapses.MEPC 61/2/10 Annex, page 34

I:\MEPC\61\2-10.doc Figure 3.1-1: SPO-SYSTEM principle

3.1.2 SPO-SYSTEM flow

Each component constituting this BWMS is installed in the engine room (pump room for a tanker), PO storage tank room and control room . Figure 3.1-2 shows a flow chart when this BWMS ballasting (a) and de-ballasting (b). Dosing of 80mg of PO against 1L of seawater Ballast

Tank

Special

Pipe

PO Injector Ballast Pump PERACLEAN ® Ocean
component

Peracetic acid (CH 3 COOOH)

Hydrogen peroxide (H 2 O 2 )

Acetic acid (CH 3 COOH)

Water (H 2 O) Principle of sterilizing of Special Pipe

Sterilizing effect by the shearing force at forward slit plate Sterilizing effect by Cavitation crash at after slit plate

Fwd

Slit

Plate Aft

Slit

Plate Fwd

Slit

Plate

Sea

Water

Sea

Chest PO

STORAGE

TANK

※ PO

・・・ PERACLEAN Æ OceanMEPC 61/2/10 Annex, page 35

I:\MEPC\61\2-10.doc Figure 3.1-2 (a): SPO-SYSTEM in ballasting

Figure 3.1-2 (b): SPO-SYSTEM in de-ballasting 1. Filter 4. Special Pipe 7. PO Storage Tank 10. Control Panel 2. PO Injector 5. Back Wash Pump 8. PO Injection Pump 11. PAA Conc. Meter 3. Ballast Pump 6. Press. Transmitter 9. PO Flow Meter

1. Filter 4. Special Pipe 7. PO Storage Tank 10. Control Panel 2. PO Injector 5. Back Wash Pump 8. PO Injection Pump 11. PAA Conc. Meter 3. Ballast Pump 6. Press. Transmitter 9. PO Flow Meter Strainer (Yard)

Strainer (Yard) Sea Chest Overboard

Overboard ENGINE ROOM PO STORAGE

TANK ROOM CONTROL ROOM

Ballast

Tank

4 10 7 8

3 1 9

6 11 5 2 6 Strainer (Yard)

Strainer (Yard) Sea Chest Overboard

Overboard

4 10 7 8

3 1 2 9

6 ENGINE ROOM PO STORAGE

TANK ROOM CONTROL ROOM

Ballast

Tank

6 11 5MEPC 61/2/10 Annex, page 36

I:\MEPC\61\2-10.doc 3.2 The manner of application (G9: 4.2.6 and 7)

3.2.1 PERACLEAN Æ Ocean

3.2.1.1 The maximum dosage concentration

PERACLEAN Æ Ocean is injected to give its concentration 80 mg/L in ballast water. This

PERACLEAN Æ Ocean injection amount is automatically controlled for the flow rate of ballast water and the injection concentration is kept to be 80 mg/L even if the ballast water flow rate varies. An injection concentration of 80 mg/L is approximately half of that of 150 mg/L when Evonik Degussa was granted Basic Approval.

In addition, various tests required for Procedure (G9) application of this BWMS were conducted with an injection concentration of 150 mg/L of PERACLEAN Æ Ocean. This is because the influence level on the hulls, crews and the environment is evaluated more strictly than the influence caused by an actual use of the PERACLEAN Æ Ocean injection concentration of 80 mg/L and this system is ensured in practical operation with greater allowance for safety. This means that a concentration of 150 mg/L is adopted for verification of influence on the environment and 80 mg/L is adopted for an actual operating system.

3.2.1.2 Holding time

The holding time in the ballast tank for ballast water treated by this BWMS should be 24 hours after which no PAA is detected even under any environmental condition. This holding time of 24 hours is the same as the holding time when Evonik Degussa was granted a Basic Approval.

3.2.1.3 The maximum allowable discharge concentration

The maximum allowable discharge concentration of Active Substance for this BWMS is specified as follows:

.1 When the tank holding time is 24 hours as described above, it has been

confirmed that the concentration of PAA falls below the detection limit (0.5 mg/L) under any environmental condition. Accordingly, little PAA (less than 0.5 mg/L) is contained in the ballast water discharged by operation of

this BWMS. The concentration of PAA below the detection limit is the same as the condition when Evonik Degussa was granted Basic Approval. Therefore, it is provided that the maximum allowable discharge concentration of PAA is less than 0.5 mg/L. Furthermore, when ballast water is discharged, PAA contained in the ballast water is monitored by a PAA

concentration meter and PAA is confirmed to be below the detection limit.

.2 The concentration of H 2 O 2 should be below 12 mg/L, which is contained in

PERACLEAN Æ Ocean with an injection concentration of 80 mg/L. The maximum allowable discharge concentration of 12 mg/L of H 2 O 2 is approximately half of the 21 mg/L when Evonik Degussa was granted Basic Approval.

.3 Then, the maximum allowable discharge concentrations of Relevant Chemicals should be the following concentrations obtained by adding a 95% confidence limit value to the concentrations (average value of 3 replicate determinations) immediately after treatment which recorded the highest concentration among time-dependent data measured in theMEPC 61/2/10 Annex, page 37

I:\MEPC\61\2-10.doc conducted test (section 5.2.2.7 of this document). In addition, the

maximum allowable concentrations of these Relevant Chemicals were not set when Evonik Degussa was granted Basic Approval. This BWMS generates a little concentration of Relevant Chemicals, however, for these trihalomethanes, the maximum allowable concentration is also set and assessed against the environmental risk. See below:

Bromoform: 14.5 μ g/L

Dibromochloromethane: 1.75 μ g/L

Bromodichloromethane: 0.31 μ g/L

4 MATERIAL SAFETY DATA SHEETS

MSDS for PERACLEAN Æ Ocean as the Preparation, PAA and H 2 O 2 as Active Substances

and Relevant Chemicals of this BWMS are contained in the confidential document.

5 RISK CHARACTERIZATION

5.1 Screening for persistence, bioaccumulation and toxicity (G9: 5.1)

5.1.1 Persistence (G9: 5.1.1.1)

Persistence (P)

Since the half-lives of PAA and H 2 O 2 , Active Substances of PERACLEAN Æ Ocean are several minutes to several days in the environment, both compounds are readily degradable and not persistent in the environment.

On the other hand, bromoform, bromodichloromethane and dibromochloromethane of Relevant Chemicals are not degradable and have the persistence.

5.1.2 Bioaccumulation (G9: 5.1.1.2)

Bioaccumulation (B)

Due to the high water-solubility and low octanol-water partition coefficient (log Pow; < 0), there is no anxiety of bioaccumulation for PAA and H 2 O 2 , Active Substances of

PERACLEAN Æ Ocean.

Meanwhile it is not supposed that there is any bioaccumulative potential for bromoform, bromodichloromethane, dibromochloromethane of Relevant Chemicals based on their BCH and log Pow values described in section 2.4.2 of this document.

5.1.3 Toxicity test (G9: 5.1.2.3)

Toxicity (T)

Toxicity is judged by using a chronic toxicity value (NOEC < 0.01 mg/L) for aquatic organisms.

As for Active Substances, PAA has the Toxicity because its NOEC is less than 0.01 mg/L. However, it is not listed as an endocrine disruptor, and carcinogenicity, mutagenicity or reprotoxicity is not found in in vitro mammalian tests.

H 2 O 2 does not have toxicity because its NOEC is 0.1 mg/L.MEPC 61/2/10 Annex, page 38

I:\MEPC\61\2-10.doc As for the Relevant Chemicals, bromoform does not have toxicity because the chronic toxicity value (NOEC) is 4.8 mg/L.

Bromodichloromethane does not have toxicity bec ause the chronic toxicity value (NOEC) is 0.78 mg/L.

Dibromochloromethane does not have toxicity, bec ause the chronic toxicity value (NOEC) is 0.063 mg/L.

5.1.4 Does the Active Substance and/or preparation meet all three criteria for PBT?

Active Substances of PERACLEAN Æ Ocean and Relevant Chemicals of this BWMS do not meet the PBT criteria specified in the Methodology (MEPC 56/2/2, annex 4) and Procedure (G9) (MEPC 57/21, annex 1). Therefore these compounds do not meet PBT compounds.

Table 5.1-1: PBT concerning Active Substances and Relevant Chemicals

Persistent (y/n) Bioacumulativ e (y/n) Toxic (y/n) Reference/Comments/

Justification for

missing data

PBT criteria Half-life: > 60 days in marine water, or > 40 days in fresh water,* or > 180 days in marine sediments, or > 120 days in fresh

water sediments Experimentally

determined BCF > 2,000, or if no experimentally

BCF has been determined, log Pow;3 Toxicity

Chronic

NOEC < 0.01 mg/L

PAA N N Y See sections 2.2.2.1,

2.4.2 and 2.4.3 in this

document

H 2 O 2 N N N See sections 2.2.2.2,

2.4.2 and 2.4.3 in this

document

Bromoform Y N N See sections 2.2.2.3,

2.4.2 and 2.4.3 in this

document

Bromodichloro

methane Y N N See sections 2.2.2.3,

2.4.2 and 2.4.3 in this

document

Dibromochloro

methane Y N N See sections 2.2.2.3,

2.4.2 and 2.4.3 in this

document

* For the purpose of marine environmental risk as sessment half-life data in fresh water and fresh water sediment can be over ruled by data obtained under marine conditions.

5.2 Evaluation of the treated ballast water (G9: 5.2)

5.2.1 Basic Approval

This BWMS uses a Preparation, PERACLEAN Æ Ocean which was reviewed at the first meeting of GESAMP-BWWG held from 23 to 27 January 2006 and was granted Basic Approval at MEPC 54 from 20 to 24 March, 2006. Meanwhile, the injection concentration was 150 mg/L when the Basic Approval was granted. This BWMS is applying 80 mg/L of injectionMEPC 61/2/10 Annex, page 39

I:\MEPC\61\2-10.doc concentration, which is almost half of that used for the Basic Approval. Active Substances

were identified as PAA and H 2 O 2 for the Basic Approval, and their risk was assessed. In this BWMS, PAA and H 2 O 2 are also identified as Active Substances and their risks are assessed. The maximum allowable discharge concentration of H 2 O 2 is 12 mg/L which is almost half of 21 mg/L for Basic Approval. On the other hand, there was no substance corresponding Relevant Chemicals according to the Basic Approval. However, since generation of a little amount of trihalomethanes is confirmed in this BWMS, they are identified as Relevant Chemicals and subjected to risk assessment.

5.2.2 Final Approval

5.2.2.1 Performed tests

The following seven tests were performed for Final Approval using this BWMS:

.1 confirmation test of by-products using the full-scale land-based test facility;

.2 Active Substances degradation test using the full-scale land-based test facility (Part 1: Storage in Simulated ballast Tank);

.3 Active Substances degradation test using the full-scale land-based test facility (Part 2: Storage in Temperature Controlled Container);

.4 change with time test of by-products using the downscaled land-based test facility;

.5 full-scale toxicity test (acute and chronic);

.6 corrosion test using the full-scale land-based test facility; and

.7 corrosion test with high-concentration PERACLEAN Æ Ocean using the full-scale land-based test facility.

5.2.2.2 Test facility

The tests for the Final Approval were performed using the test facility of SPO-SYSTEM for Guidelines (G8) land-based test (treatment flow rate: 200 m 3 /h). Only the downscaled land-based test facility of SPO-SYSTEM was us ed for "SPO-SYSTEM Change with Time Test of By-products".

5.2.2.3 Test site

Test site is the coastal facility in Imari city, Saga Prefecture in the Southwest Japan.

The land-based test facility mainly consists of simulated ballast tanks (200 m 3 ) (a barge was moored at the public quay and divided into four sections), a ballast pump and this BWMS.

5.2.2.4 Confirmation test of by-products using the full-scale land-based test facility

This test was carried out to confirm the kind and the amount of by-products (Relevant Chemicals) which were produced by the treatment using this BWMS.

With regard to trihalomethanes, 1.9 to 7.8 μ g/L of bromoform, 0.2 to 0.9 μ g/L of chlorodibromomethane and only in some test, 0.1 μ g/L of bromodichloromethane wereMEPC 61/2/10 Annex, page 40

I:\MEPC\61\2-10.doc detected. These concentrations were higher in brackish water than in seawater. Furthermore, 0.4 μ g/L of chloroform was detected in both untreated and treated water only in

one test.

On the other hand, halogenated phenols were not detected in every test group. Although AOX was also detected only in treated water this value was the total amount of absorbable halogenated organic compounds and not determined as specific compounds. And it was

detected more in the case of brackish water criteria than seawater criteria.

Bromoform, chlorodibromomethane and a small amount of bromodichloromethane were produced in the water which is treated by this BWMS with 80 or 150 mg/L of PERACLEAN Æ
Ocean. According to the test results, it was determined that these three compounds were subjected to risk assessment.

5.2.2.5 Active Substances Degradation Test using the full-scale land-based test facility (Part 1: storage in simulated ballast tank)

By using the full-scale land-based test facility of this BWMS, we have carried out treatment of seawater and brackish water under the condition specified in Guidelines for approval of ballast water management systems (G8), wh ich confirmed the degradation of PAA and H 2 O 2

.

The results of tests satisfying seawater criteria showed that concentration of PAA and H 2 O 2 reached below the lower detection limit (0.5 mg/L) within 21 hours and 45 to 117 hours, respectively. It is presumed that the difference of water temperature at each test affected the degradation rate of H 2 O 2 . On the other hand, the results of tests satisfying seawater criteria

showed that concentration of PAA and H 2 O 2 reached below the lower detection limit within 21 to 24 hours and 51 to 69 hours, respectively.

With these test results, we confirmed that the peracetic acid degraded within 24 hours, of which concentration reached below the lower detection limit in ballast water treatment by SPO-SYSTEM using 80 mg/L of PERACLEAN ® Ocean. And it was also confirmed that the

concentration of H 2 O 2 reached below the lower detection limit within 5 days holding time (120 hours). Furthermore, 5.4 and 9.6 mg/L of H 2 O 2 were calculated as the lower and upper limit of 95% confidence interval, which remained 24 hours after the treatment.

5.2.2.6 Active Substances degradation test using the full-scale land-based test facility (Part 2: storage in temperature controlled container)

The objective of this test is to investigate effects of the existence of particulate substance and the temperature on the degradation behaviour of PAA and H 2 O 2 in the simulated ballast water which was prepared by means of carrying out a treatment fulfilling seawater and brackish water by using the full-scale land-based test facility of this BWMS.

PAA degraded most quickly, which was stored at 20oC, and its concentration reached below the lower detection limit (0.5 mg/L) within 4 hours in seawater and 10 to 12 hours in brackish water. Along with the storage temperature decreased, the degradation rate slowed down. In case of storage at 5oC, it took 10 to 12 hours in seawater and 24 hours in brackish water. Furthermore the rate showed a tendency to slow down in brackish water rather than in seawater. On the other hand, there was no significant difference of degradation rate depending on the filtration.

The degradation rate of H 2 O 2 also slowed along with the decrease of the storage temperature and the slowest was observed in filtered brackish water and stored at 5oC,

which took 380 hours not to be detected.MEPC 61/2/10 Annex, page 41

I:\MEPC\61\2-10.doc Above results concluded that the concentration of PAA reached below the lower detection limit (0.5 mg/L) within 24 hours in the simulated ballast water (brackish water) which was treated by this BWMS with 80 mg/L of PERACLEAN Æ Ocean and was stored at 5oC, i.e. the temperature required longest time not to be detected. As for H 2 O 2 , the degradation rate slowed down in the same conditions, and it was confirmed to require 380 hours not to be detected (< 0.5 mg/L).

From the foregoing and the test results described in section 5.2.2.5 of this document, it is

evaluated that PAA concentration reached below the detection limit under cold condition, e.g., at 5oC, such temperature delays the degradation of PAA. Meanwhile the half-life of

H 2 O 2 was approximately 24 hours under the same condition; its degradation rate was fast.

5.2.2.7 Change with time test of by-products using the downscaled land-based test facility

This test was conducted to confirm the degradability of by-products (Relevant Chemicals) under the brackish water criteria specified in the Guidelines for approval of ballast water management systems (G8).

The results revealed that 12 μ g/L (upper limit: 14.5 μ g/L) of bromoform was detected right after the treatment, which was the highest concentration among trihalomethanes, and furthermore, 1.5 μ g/L (upper limit: 1.75 μ g/L) of dibromochloromethane and 0.2 μ g/L (upper

limit: 0.31 μ g/L) of bromodichloromethane were detected. No significant decay of by-products was observed within 5 days after the treatm ent. Consequently, it was confirmed that Relevant Chemicals did not degrade or degrade much slowly. This follows the existing data.

5.2.2.8 Full-scale toxicity test (acute and chronic)

This test was performed to get hold of the acute and chronic toxicity of the ballast water discharge, which is treated by this BWMS, for algae, invertebrates and fish.

5.2.2.8.1 Acute toxicity test

.1 Seawater test

See section 2.2.1.4(1) of this document.

.2 Brackish water test

See section 2.2.1.4(2) of in this document.

5.2.2.8.2 Chronic toxicity test

.1 Seawater test

See section 2.2.2.4(1) of this document.

.2 Brackish water test

See section 2.2.2.4(2) of this document.MEPC 61/2/10 Annex, page 42

I:\MEPC\61\2-10.doc 5.2.2.9 Corrosion test using the full-scale land-based test facility

This test was conducted to evaluate the corrosive influence of the ballast water on ballast tank coatings and uncoated materials. The ballast water used was prepared by land-based test facility of this BWMS with 80 mg/L of the PERACLEAN Æ Ocean injection rate as same as that of actual operation of this BWMS.

The test results indicated that there is no or only allowable corrosive influence of treated water on the ballast tank coatings and uncoated materials.

5.2.2.10 Corrosion test with high-concentration PERACLEAN Æ Ocean using the full-scale land-based test facility

This test was conducted to evaluate the corrosive influence of the ballast water on ballast tank coatings and uncoated materials over the period of 6 months. The ballast water used was prepared by land-based test facility of th is BWMS with 150 mg/L of the PERACLEAN Æ
Ocean injection rate almost as twice as that of actual operation of this BWMS. Thus severe condition was applied.

The test results indicated that there is no or only allowable corrosive influence of treated water on the ballast tank coatings and uncoated materials in the same way of 80 mg/L.

5.2.3 Determination of holding time

Holding time of this BWMS is set at least 24 hours, within which PAA concentration reaches under the lower detection limit (0.5 mg/L) in all tests described in section 5.2.2 of this document. This holding time is the same as that has been granted Basic Approval.

5.3 Risk characterization and analysis

5.3.1 Reaction with organic matter (G9: 4.2.1.3)

As for reaction with organic matter, it was confirmed with analysis of the ballast water before and after the treatment by using the full-scale land-based test facility. As the results, while an increase of AOX was observed, it could be said that the reason for this was the addition of a high-concentration of organic matter, in order to fulfill water quality criteria of Guidelines (G8) land-based test.

In addition, generation of small amount of trihalomethanes was confirmed in various tests. It is supposed that their generation is due to the reaction of hypobromous acid, which is trihalomethanes precursor and an intermediate product, with organic matter. According to these results, trihalomethanes are considered as Relevant Chemicals and subjected to risk assessment in this application. As shown in section 5.3.8 of this document, their effects on the aquatic environment were at the negligible levels.

5.3.2 Characterization of degradation route and rate (G9: 5.3.5)

PAA and H 2 O 2 , Active Substances of PERACLEAN Æ Ocean, readily degrade in the environmental media. Abiotic degradation half-lives in seawater are in the range of several minutes for PAA, and up to 48 hours in fresh water at pH 4 to 7. For H 2 O 2 , half-lives of several hours up to 5 days were predicted under environmental conditions. The half-life will be more rapid in the presence of transitions metals, metal oxides and hydroxides, at Ph Values > 7. Heat and sunlight can induce photochemical decomposition. However,

it should also be considered that H 2 O 2 is also generated photochemically in water systems.MEPC 61/2/10 Annex, page 43

I:\MEPC\61\2-10.doc Both PAA and H 2 O 2 are readily biodegradable with half-lives with sewage treatment plant inoculum of 2 to 3 minutes if the toxicity levels are not superseded.

Degradation of PERACLEAN Æ Ocean results only in the formation of oxygen and water as well as acetic acid that can be readily metabolised, yielding carbon dioxide and water. No persistent metabolites are formed. A half-life with the abiotic degradation of PAA is a few minutes.

It was confirmed that the concentrations of PAA, an Active Substance reached below the detection limit (0.5 mg/L) within 24 hours under any conditions and the concentration of H 2 O 2 became approximately half in the degradation tests conducted for the application for Final Approval (sections 5.2.2.5 and 5.2.2.6 in this document). However, there was hardly any degradation of the Relevant Chemicals in cluding bromoform, bromodichloromethane and

dibromochloromethane under the examined aerobi c conditions (section 5.2.2.7 of this document).

5.3.3 Prediction of discharge and environmental concentrations

Predicted environmental concentrations (PEC) for H 2 O 2 of Active Substance and bromoform, bromodichloromethane, and dibromochloromethane of Relevant Chemicals in the ballast water discharged from this BWMS were calculated by using MAMPEC model version 2.0 targeting on Tokyo Bay.

Table 5.3-1 shows the calculation results of PEC.

Table 5.3-1: PEC calculation results in designated sea area using MAMPEC model, ver. 2.0

5.3.4 Assessment of potential for bioaccumulation

Due to the low octanol-water partition coefficients (log Kow = -0.26 for PAA and -1.5 for H 2 O 2 ),

PERACLEAN Æ Ocean does not possess a bioaccumulative potential. Therefore, assessment of bioaccumulation is not necessary.

On the other hand, as mentioned in section 2.4.2 of this document, log Kow values of Relevant Chemicals generated by this BWMS including bromoform, bromodichloromethane and dibromochloromethane are 2.4, 2.1 and 2.24, respectively, and all of them are lower than log Kow: 3, an index which induces the bioaccumulation. Consequently, it is assumed that there is no risk on bioaccumulation of the Relevant Chemicals discharged by this

BWMS. PEC of Relevant Chemicals (μg/ L) PEC of H 2 O 2 (μg/ L) Bromoform Dibromochloromethane Bromodichloromethane

Maximum

concentration 4.72E-01 1.47E-03 1.71E-04 2.87E-05

95%

concentration 4.66E-01 1.35E-03 1.57E-04 2.65E-05

Average

concentration 2.17E-01 8.54E-04 9.92E-05 1.65E-05

Median

concentration 1.75E-01 8.44E-04 9.79E-05 1.61E-05

Minimum

concentration 3.66E-02 1.84E-04 2.13E-05 3.53E-06MEPC 61/2/10 Annex, page 44

I:\MEPC\61\2-10.doc 5.3.5 Effects assessment

In this BWMS, the maximum discharge concentration of an Active Substance, H 2 O 2 is 12 mg/L, and those of Relevant Chemicals, bromoform, dibromochloromethane and bromodichloromethane are 0.0145 mg/L, 0.00175 mg/L and 0.00031 mg/L, respectively.

As for H 2 O 2 , because the acute and chronic toxicity value is 1.38 mg/L and 0.1 mg/L, respectively, the ballast water discharge has an aquatic toxicity. However, due to its high degradation rate, and diffusion and dilution after the discharge, its concentration should become acceptable level. As for Relevant Chem icals, their concentrations in ballast water discharge are much less than the values that show the acute and chronic toxicity. Accordingly, there is no risk of toxicity.

Taking in consideration of the physicochemical properties of these compounds, there is no bioaccumulative potential. Therefore the accumulative toxic effects are unlikely via food-web.

5.3.6 Effects on aquatic organisms

5.3.6.1 Estimated PNEC

The PNEC of Active Substance and Relevant Chemicals discharged from the SPO-SYSTEM

is estimated as follows:

.1 H 2 O 2 : 0.01 mg/L of PNEC have been obtained in MEPC 57/2/10 already.

.2 Bromoform: LC 50 or EC 50 have been obtained for 5 species of marine species and 4 species of fresh water species. Furthermore MATC and/or NOEC have been obtained for 2 fresh water species in total and the lowest concentration is 12 mg/L of 96h-LC 50 for seawater and 4.8 mg/L of MATC for fresh water. By setting the assessment factors in this case to 1000 (long) and 100 (short), the results are 12 μ g/L for PNEC seawater (long), 120 μ g/L for PNEC seawater (short), 4.8 μ g/L for PNEC fresh water (long)

and 48 μ g/L for PNEC fresh water (short).

.3 Bromodichloromethane: LC 50 or EC 50 have been obtained for 6 fresh water species, and NOEC have been obtained for 3 fresh water species in total and the lowest concentration is 11.6 mg/L of EC 50 for algae and 0.78 mg/L of NOEC for fish. By setting the assessment factors in this case to 100 for seawater and 10 for fresh water, the results are 7.8 μ g/L for PNEC seawater and 78 μ g/L for PNEC fresh water

.

.4 Dibromochloromethane: LC 50 or EC 50 have been obtained for 6 fresh water species, and NOEC have been obtained for 3 fresh water species in total and the lowest concentration is 9.6 mg/L of EC 50 for algae and 0.063 mg/L of NOEC for crustacean. By setting t he assessment factors in this case to 100 for seawater and 10 for fresh water, the results are 0.63 μ g/L for

PNEC seawater and 6.3 μ g/L for PNEC fresh water

.

5.3.6.2 PEC/PNEC ratio

Based on the PEC obtained in section 5.3.3 of this document and the PNEC estimated in section 5.3.6.1 of this document, PEC/PNEC was calculated. The results are shown in

Table 5.3-2.

PEC/PNEC of H 2 O 2 and Relevant Chemicals discharged from the SPO-SYSTEM were far

lower than 1.MEPC 61/2/10 Annex, page 45

I:\MEPC\61\2-10.doc Accordingly, the toxicity of H 2 O 2 was reflected in the toxicity test results (section 5.2.2.8 of this document), however, it was estimated that the dilution and degradation effects made its environmental risk acceptable.

Table 5.3-2: PEC, PNEC and PEC/PNEC ratio

Relevant Chemicals PEC (μg/ L) PNEC (μg/L) PEC/PNEC

H 2 O 2 0.217 10 0.0217

long short long short Bromoform 0.000854 12 120 7.12E-05 7.12E-06

Dibromochloromethane 0.0000992 7.8 1.27E-05

Bromodichloromethane 0.0000165 0.63 2.62E-05

5.3.7 Effects on sediment

As described in section 2.2.4 of this document, adsorption on sediment and persistence are not supposed for all of H 2 O 2 and Relevant Chemicals discharged by this BWMS. Therefore,

it is considered that there is no effect on sediment.

5.3.8 Comparison of effect assessment with discharge toxicity

The toxicity of H 2 O 2 was reflected in the results of the toxicity tests. Nevertheless it was assumed that such risk was acceptable in the actual sea area because of the dilution and degradation after discharge of the ballast water.

6 RISK ASSESSMENT

6.1 Risk to safety of ship

6.1.1 Increased corrosion

As stated in sections 5.2.2.9 and 5.2.2.10 of this document, the results of the corrosion testing using the Guidelines (G8) full-scale land-based test facility indicate that the corrosive influence of the treated water prepared by this BWMS on the coating materials of the ballast

tank and various materials is allowable.

In consideration of the nature of PERACLEAN Æ Ocean, it is unlikely that there is a fire hazard. Furthermore, although PERACLEAN Æ Ocean possesses an explosive potential at high temperature (> 60oC), a storing method to maintain at 35oC or lower is adopted. If the temperature exceeds 35oC, the suffici ent safety precautions are given.

6.1.3 Storage and handling of the substances

As for storage, filling, production and supply of PERACLEAN Æ Ocean, full countermeasures are devised to remove any risks.

6.1.4 Contact with, or inhalation of, process products

As for contact inhalation, full countermeasures are devised to remove any risks. Moreover it is assessed that this BWMS is safe for ship as described in section 6.2 of this document (vide infra).MEPC 61/2/10 Annex, page 46

I:\MEPC\61\2-10.doc 6.1.5 Noise

It is not supposed that the operation of this BWMS generates noise.

6.2 Risk to human health

6.2.1 Health effects in humans (G9: 5.3.12)

The health effect scenario in humans (except for shipboard personnel) is estimated by consideration of the seafood web and the ecosystem. As the ballast water discharge from this BWMS is unlikely to cause any impact on the environment, however, this route has a little risk. Relevant Chemicals are potentially dissipated from the ballast tank. When the Relevant Chemicals were measured, they were detected at low concentrations and were not at a level to affect human health. Therefore, volatile trihalomethanes have no risk to human

health.

Although residual PAA and H 2 O 2 in the ballast water in the case of their slow degradation are unlikely to affect human health during inspection of the ballast tank, protective equipments should been worn during inspection to avoid any risk.

Health effects in humans were summarized as follows, making reference to the method specified in document MEPC 57/2/10, annex 4, appendix 2.

6.2.2 Human Exposure Scenario (HES)

6.2.2.1 Exposure scenario-1: Exposure of shipboard personnel to Preparation when charged

The highest inhalation exposure of PAA to worker s is expected during pouring and filling by manual procedures. The application for Final Approval for another system using the same Preparation, in which 150 mg/L of the PERACLEAN Æ Ocean is used (PAA = 22.5 mg/L,

H 2 O 2 = 21.5 mg/L), showed that exposure concentration to PAA was 0.0435 mg/m 3
(MEPC 57/2/10). This value accounts for approximately 7.25% of 0.6 mg/m 3 , a TLV of PAA proposed by the application for Final Approval of another system using PERACLEAN Æ Ocean, therefore, it is concluded to be no risk of PAA to shipboard personnel (workers) (MEPC 57/2/10).

A TLV-TWA of H 2 O 2 by ACGIH is 1.4 mg/m 3 . Consequently, H 2 O 2 is considered to have little

risk as well as PAA.

On the other hand in this system, Preparation is stored in a PO storage tank at 35°C or lower temperature, which is isolated from an engine room and is injected into ballast water in filling using automatic control pump as required. Therefore, there is no risk that shipboard personnel are exposed to Preparation or its components in usual storage and injection.

Active Substances, PAA, and H 2 O 2 cause strong irritation to the skin, eyes, and respiratory systems at high concentrations; therefore, it is recommended that workers wear respirator, gloves and glasses, and protective clothing when they can be exposed to Active Substances.

6.2.2.2 Exposure scenario-2: Exposure to vaporized Preparation in ballast tank after charge for shipboard personnel

In this system, it is assumed that Preparation of 80 mg/L is added into ballast water and held for 1 to 2 days. Active Substances, PAA and H 2 O 2 , degrade in ballast water and Relevant Chemicals generate simultaneously. Considering that Active Substances quickly degrade inMEPC 61/2/10 Annex, page 47

I:\MEPC\61\2-10.doc water and they should be diluted in air phase in the ballast tank, exposure concentration of Active Substances under this scenario should be lower than the scenario-1 "filling and loading in manual operation". Consequently, no health risk of Active Substances is expected.

However, Relevant Chemicals generated in ballast water are assumed to be volatilized into the air in a ship. Therefore, a model for distribution into the ship air from ballast water by volatilization was estimated using Mackey Level III of EPI SUITE V3.2. In the estimation by modelling, a release velocity into each environment al media (air/water/soil) is set at 0/1000/0 and other setting values were used as default ones of the model.

The model-estimated results of environmental distribution showed that 14-18% of Relevant Chemicals were distributed in the air. On the basis of the above estimation results, the concentrations of Relevant Chemicals in air phase in ballast tank is under the worst case, where the conditions of air ventilation rate of air phase in ballast tank of 0 is calculated. The content volumes of ballast water and air phase of ballast tank are assumed to be 15,000 and 5,000 m 3 , respectively, which are general values.

6.2.2.3 Exposure scenario-3: Exposure of general public after discharge of ballast

water

The exposure scenarios of general public after ballast water is discharge after treatment with this BWMS include: (1) exposure by vaporizat ion from seawater, (2) indirect exposure through seafood via food chain, and (3) direct exposure to seawater of sea-bathers and

fishermen. See below:

.1 The risk to shipboard personnel that was assumed in a closed ballast tank is little, therefore, health risk in general environment can be ruled out.

.2 The octanol-water partition coefficients of all Active Substances and Relevant Chemicals are less than 3, therefore, it is concluded that there is no concern about exposure via food chain.

.3 Active Substances and Relevant Chemicals at concentrations in ballast water have no concern about irritation. The initial (maximum) concentration of Active Substance, PAA, in ballast water was 13.6 mg/L and in comparison with the NOAEL of PAA in animal study of 1.7 mg/kg/day, (although this exposure scenario is unrealistic) the concentration is correspondent to the volume of 7.5 L or more of seawater for humans (body weight: 60 kg). Furthermore, PAA and H 2 O 2 , Active Substances, relatively degrade rapidly and ballast water is diluted after discharge, therefore, it is concluded to have no risk for human health. In addition,

Relevant Chemicals had no risk for human health to be concerned.

6.2.3 Considered analysis

Under normal conditions of using this BWMS, it is considered that Active Substances and Relevant Chemicals have no health risk to shipboard personnel and general public.

6.3 Risk to the aquatic environment

As summarized in section 5 of this document, there is little effect on the environment as a result of the ballast water discharge of this BWMS.MEPC 61/2/10 Annex, page 48

I:\MEPC\61\2-10.doc 7 CONCLUSION

This BWMS uses PERACLEAN Æ Ocean with an injection concentration of 80 mg/L as a Preparation. This injection concentration is almost half of 150 mg/L used for the Basic Approval (see MEPC 53/2/12). PAA as an Active Substance is put under surveillance by a PAA concentration meter so as not to exceed the detection limit when discharged.

With reference to the use of PERACLEAN Æ Ocean, the result of various tests implemented in a full-scale land-based test facility as well as the risk assessment on the environment, human beings and ships showed that the risks against them were within acceptable ranges. From this point of view this BWMS deserves Final Approval.

8 REFERENCES

ACGIH 2001. Documentation of the TLVs and BEIs. Bromoform.

ATSDR 1989. Toxicological Profile for Bromodichloromethane.

ATSDR 2005. Toxicological Profile for Bromoform and Dibromochloromethane. U.S. Department of health and human services.

ECETOC-JACC 2001. Peracetic Acid (CAS No . 79-21-0) and its Equilibrium Solutions.

JACC No.40.

EU-RAR 2003. European Union Risk Assessment Report. Hydrogen peroxide.

IARC 1991a. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to

Human. Bromodichloromethane.

IARC 1991b. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to

Human. Dibromochloromethane.

IARC 1999a. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Human. Hydrogen peroxide.

IARC 1999b. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to

Human. Bromoform.

IARC 1999c. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to

Human. Bromodichloromethane.

IARC 1999d. Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to

Human. Chlorodibromomethane.

IPCS-EHC 2000. Environmental Health Criteria 216. Disinfectants and disinfectant by-products.

IPCS-ICSC 1999. International Chemical Safety Cards #1031 Peracetic acid.

IPCS-ICSC 2005a. International Chemical Safety Cards #0164 Hydrogen peroxide.

IPCS-ICSC 2006. International Chemical Safety Cards #0393 Bromodichloromethane.MEPC 61/2/10 Annex, page 49

I:\MEPC\61\2-10.doc JIS K0125 1995. Testing methods for volatile organic compounds in industrial water and

waste water.

JIS K1463 2007. Hydrogen Peroxide.

NITE 1986. Biodegradation and Bioconcentration of Existing Chemical Substances under

the Chemical Substances Control Law.

Nurizzo U, et al. , 2005. By-products in surface and reclaimed water disinfected with various agents, Desalination, 176 (567-571)

Pinkernell U, et al., 1997. Selective Photometric Determination of Peroxycarboxylic Acids in the Presence of Hydrogen Peroxide. Analyst, June 1997, Vol. 122 (567ñ571)

US EPA ECOTOX 2007. Bromoform.

US EPA ECOTOX 2009. Bromodichloromethane.

US NLM HSDB 2002. Hazardous Substance Data Bank. Peracetic acid.

US NLM HSDB 2009a. Hazardous Subs tance Data Bank. Bromoform.

US NLM HSDB 2009b. Hazardous Substance Data Bank. Bromodichloromethane.

US NLM HSDB 2009c. Hazardous Substance Data Bank. Dibromochloromethane.

US NLM HSDB 2009d. Hazardous Substance Data Bank. Hydrogen Peroxide.

US NTP 1989. TOXICOLOGY AND CARCINOGENESIS STUDIES OF TRI-BROMOMETHANE (BROMOFORM).

USGS 2007. FINDING OF NO SIGNIFICANT IMPACT for Hydrogen Peroxide for Control of Mortality in Fresh water Finfish and Finfish Eggs Due to External Fungal and Bacterial

Diseases.

Zepp RG, et al. , 1987. Algal-induced Decay and Formation of hydrogen Peroxide in Water: Its Possible Role in Oxidation of Anilines by Al gae. Phytochemistry of Environment Aquatic Systems, 327 (215-224).

LIST OF APPENDICES

APPENDIX 1 STATEMENT

APPENDIX 2 QUALITY ASSURANCE STATEMENT

APPENDIX 3 QUALITY ASSURANCE PROJECT PLAN (QAPP) FOR

CORROSION TESTING OF SPO-SYSTEM

APPENDIX 4 QUALITY MANAGEMENT PLAN (QMP) AND QUALITY ASSURANCE PROJECT PLAN (QAPP) FOR ANALYSIS OF

BALLAST WATER TREATED BY SPO-SYSTEM

* * *MEPC 61/2/10 Annex, page 50

I:\MEPC\61\2-10.doc APPENDIX 1

STATEMENT

* * *MEPC 61/2/10 Annex, page 51

I:\MEPC\61\2-10.doc APPENDIX 2

QUALITY ASSURANCE STATEMENTMEPC 61/2/10 Annex, page 52

I:\MEPC\61\2-10.doc * * *MEPC 61/2/10 Annex, page 53

I:\MEPC\61\2-10.doc APPENDIX 3

QUALITY ASSURANCE PROJECT PLAN (QAPP) FOR CORROSION TESTING

OF SPO-SYSTEM



## Extracted versionMEPC 61/2/10 Annex, page 54

I:\MEPC\61\2-10.docMEPC 61/2/10 Annex, page 55

I:\MEPC\61\2-10.docMEPC 61/2/10 Annex, page 56

I:\MEPC\61\2-10.doc APPENDIX 4

QUALITY MANAGEMENT PLAN (QMP) AND QUALITY ASSURANCE PROJECT PLAN (QAPP)

FOR ANALYSIS OF BALLAST WATER TREATED BY SPO-SYSTEMMEPC 61/2/10 Annex, page 57

I:\MEPC\61\2-10.docMEPC 61/2/10 Annex, page 58

I:\MEPC\61\2-10.doc _____________