I:\MEPC\61\2-8.doc 

# E

MARINE ENVIRONMENT PROTECTION

COMMITTEE

61st session Agenda item 2 MEPC 61/2/8

28 March 2010 Original: ENGLISH

HARMFUL AQUATIC ORGANISMS IN BALLAST WATER

Application for Final Approval of the Ecochlor ®

Ballast Water Management System

Submitted by Germany

SUMMARY

Executive summary: This document contains the non-confidential information related to the application for Final Approval of the Ecochlor ®

Ballast Water Management System under the "Procedur e for approval of ballast water management systems that make use of Active Substances (G9)" adopted by resolution MEPC.169(57)

Strategic direction: 7.1

High-level action: 7.1.2

Planned output: 7.1.2.4

Action to be taken: Paragraph 6

Related documents: BWM/CONF/36; MEPC 57/21; MEPC 58/23; MEPC 59/2/9; MEPC 60/2/11; BWM.2/Circ.13 and BWM.2/Circ.24

Introduction

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

2 Germany 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.24, this application contains the non-confidential part of the manufacturer's application dossier in the annex. The complete dossier will be made available to the experts of the GESAMP-BWWG with the understanding

of confidential treatment.MEPC 61/2/8 Page 2

I:\MEPC\61\2-8.doc 3 Basic Approval of the Ecochlor ®

Ballast Water Management System was applied for in document MEPC 58/2/2 and was granted at MEPC 58 (MEPC 58/23, paragraph 2.6.3). Final Approval, as applied for in document MEPC 59/2/9, was not granted at MEPC 60.

4 After carefully taking into account the recommendations contained in annex 5 of the Report of the tenth meeting of the GESAMP-BWWG (MEPC 60/2/11), the competent authority has again verified the application dossier and believes it to satisfy the requirements of Procedure (G9) adopted by resolution MEPC.169(57). In particular, a thorough re-evaluation of the discharge toxicity and environmental modelling has been undertaken by the Administration and has found no unacceptable environmental risk caused by the system.

5 To ease the workload of the Committee, the annex to this document is limited to the issues raised by the GESAMP-BWWG in its tenth meeting (MEPC 60/ 2/11). It should be read in conjunction with documents MEPC 59/2/9 and MEPC 60/2/11.

Action requested of the Committee

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

***MEPC 61/2/8 Annex, page 1

I:\MEPC\61\2-8.doc ANNEX

NON-CONFIDENTIAL INFORMATION OF THE ECOCHLOR ®

BALLAST WATER MANAGEMENT SYSTEM

Contents

1 INTRODUCTION

2 CHEMISTRY

2.1 Overview of chlorine-based and chlorine-dioxide-based chemistry 2.1.1 Bromide ion interaction and decomposition chemistry 2.1.2 Disinfection by-product formation 2.1.3 Hypochlorite ion and chlorite ion

2.2 Oxidant measurements

2.2.1 TRO as chlorine and DPD test method 2.2.2 Methods for measuring chlorine dioxide, chlorite ion, chlorate ion and bromate ion

2.3 Oxidant demand 2.3.1 Comparison of oxidant demand for shipboard and land-based testing

3 HYDRODYNAMIC MODELLING AND ASSESSMENT OF ENVIRONMENTAL RISK

3.1 Re-calculation of PEC values using the MAMPEC Model 3.2 Details of the modelling parameters for PEC re-calculation by Ecochlor ®

3.3 PEC re-calculation results and PEC/PNEC ratios 3.4 Maximum allowable discharge concentrations

4 DISCHARGE ECOTOXICITY

5 SHIP SAFETY AND MAINTENANCE

5.1 Corrosion and ballast tank coatings 5.2 Fire risk mitigation 5.3 Chemical storage

6 SUMMARY

7 REFERENCES

LIST OF TABLES

Table 1: Chemical analysis of ballast water treated on board

the M.V. Moku Pahu , San Francisco Bay Area (Richmond, CA) Table 2: Comparison of DBP concentrations for chlorine and chlorine dioxide

treatments Table 3: Comparison of hypochlorite ion and chlorite ion

Table 4: Ecochlor ®

chlorine dioxide demand study, 4oC

Table 5: Ecochlor ®

chlorite ion demand study, 20oC Table 6: Summary of chlorine dioxide and chlorite concentrations, land-based testing Table 7: Summary of chlorine dioxide and chlorite concentrations, shipboard testing Table 8: Chlorine dioxide decay study, shipboard testingMEPC 61/2/8 Annex, page 2

I:\MEPC\61\2-8.doc Table 9: Summary of treated ballast water substance emissions

Table 10: Re-calculated Predicted En vironmental Concentrations – MAMPEC

Table 11: Re-calculated PEC/PNEC ratios Table 12: Summary of corrosion test methods

LIST OF FIGURES

Figure 1: Chlorine species at various pH values Figure 2: Bromine species at various pH values Figure 3: Chlorine dioxide species at various pH values Figure 4: Example of chlorine dioxide demand curve, 4oC Figure 5: Example of chlorite ion demand curve, 20oC Figure 6: Chlorine dioxide decay study, shipboard testing Figure 7: Harbour definition information provided by the GESAMP-BWWG Figure 8: Emission parameter information provided by the GESAMP-BWWG Figure 9: Example of compound definition parameters

APPENDICES CONTAINED IN THE CONFIDENTIAL DOSSIER

APPENDIX 1 MAMPEC modelling documentation APPENDIX 2 Corrosion study reports APPENDIX 3 Example of Health and Safety Plan (HASP) APPENDIX 4 Chlorine dioxide analytical informationMEPC 61/2/8 Annex, page 3

I:\MEPC\61\2-8.DOC 1 INTRODUCTION

Ecochlor ®

is applying for Final Approval of the Purate ® chlorine dioxide generation method

utilized with the Ecochlor ®

Ballast Water Management System (BWMS) in accordance with the International Maritime Organization's Procedure (G9) (resolution MEPC.169(57)).

Ecochlor applied for Basic Approval (MEPC 58/2/2), which was granted at MEPC 58 (MEPC 58/23). Ecochlor ®

submitted a dossier for Final Approval in December 2008 (MEPC 59/2/9). That dossier was reviewed during the tenth meeting of the GESAMP-BWWG in September 2009 but Final Approval was not recommended.

The comments received from the GESA MP-BWWG (MEPC 60/2/11) on Ecochlor ®' s Final Approval application dossier are summarized below. Therefore, this document supports a re-submission for Final Approval and focuses on providing clarification to address the

GESAMP-BWWG concerns. This document shoul d be considered along with the original Final Approval dossier (MEPC 59/2/9).

The following is the summary of the GESAMP-BWWG comments (MEPC 60/2/11, annex 5):

.1 Having reviewed all the data and information submitted by Germany with the application for Final Approval and the information received from the applicant during the GESAMP-BWWG meeting, the Group could not recommend to MEPC that Final Approval be granted to the Ecochlor ®
Ballast Water Management System (BWMS).

Response: This submission addresses the concerns of the Group.

.2 The Group recalled that Basic Approval of the BWMS was granted by MEPC 58 and the report is available at document MEPC 58/2/8 (BWWG 7/9, annex 5, Review of Proposals for Approval of Ballast Water Management Systems that make use of Active Substances).

No response required.

.3 In view of the responses from the applicant to questions posed by the Group in the Basic Approval Report, together with the information received from the applicant during the GESAMP-BWWG meeting, the Group could accept that the information provided in the dossier supplemented by that provided by the applicant in response to questions was sufficient to enable an appropriate evaluation to be made.

No response required.

.4 The Group noted that the Ecochlor ® BWMS uses a combination of filtration and oxidation. The oxidation is performed by the reaction on board ship

between Purate ® (a propriety Preparation from Eka Chemicals containing 40% by weight sodium chlorate (NaClO 3 ) and 8% by weight hydrogen peroxide (H 2 0 2 ) in water) and sulphuric acid (H 2 SO 4 ) to generate

chlorine dioxide as Active Substance at a maximum allowable concentration of 5 mg/L to treat the ballast water by oxidation and disinfection.

No response required.MEPC 61/2/8 Annex, page 4

I:\MEPC\61\2-8.doc .5 The Group noted that the applicant has provided information on ecotoxicity testing of treated ballast water, environmental risk assessment for aquatic organisms, and a proposal for maximum allowable discharge concentrations for the Active Substances and Relevant Chemicals, together with a proposal for minimum holding time for treated ballast water. The Group noted the discharge concentrations, with a treated ballast water holding time of 24 h, were as follows:

Chlorine dioxide – 0.85mL (= 0.44 mg/L TRO as Cl 2 );

Chlorite ion – 3.8 mg/L (= 1.98 mg/L TRO as Cl 2 );

Chlorate ion – 2.4 mg/L (= 1.01 mg/L TRO as Cl 2 ); and

Dibromoacetic acid (DBAA) – 0.036 mg/L.

Response: Discussion on the applicability of TRO as Cl 2 is presented in section 2.2. Ecochlor ®

would like to note that the highest discharge concentration values presented in the Final Approval dossier for chlorite ion and chlorate ion 24 hours (1 Day) after ballast water treatment are 3.6 mg/L and 1.47 mg/L, respectively. The values summarized in the Group ' s comment are the values immediately after treatment (Day 0) (see Table T2.8a; MEPC 59/2/9).

.6 The Group noted that the applicant indicated in its dossier for Final Approval that all the discharge concentrations mentioned above were higher than had been reported in the application for Basic Approval. The Group recognized that the degradation half-life of chlorine dioxide in natural seawater is about 3 minutes. However, the chlorite and chlorate ion, which are primary by-products when chlorine dioxide degrades, are toxic to aquatic organisms. The Group considered that the discharge concentrations of chlorite and chlorate ions, which can be measured as part of the TRO, are significant in the evaluation of risks to the environment.

Response: The higher discharge concentrations presented in the prior Final Approval dossier are due to the difference in testing environments (shipboard vs. land-based) and the varying effects of oxidant demand and decay in these scenarios. See section 2.3 for discussion. With respect to TRO and the applicability to chlorine dioxide, chlorite and chlorate, Ecochlor ®

presents discussion in

section 2.2.

.7 The Group noted that the discharged ballast water contains 3.8 mg chlorite/L (= 1.98 mg/L TRO as Cl 2 ) after 24 hours holding time. The Group had concerns with this discharge concentration as very similar levels of TRO have been used as the maximum allowable dosage in other systems that have been evaluated. The Group previously recommended to other systems that a discharge concentration in the range of 0.1 mg/L to 0.2 mg/L TRO (as Cl 2 ) should be set as the maximum allowable discharge concentration (MADC). The chlorite discharge concentration exceeds the above recommendations for TRO by a factor of 19 to 38 and is thereforeMEPC 61/2/8 Annex, page 5

I:\MEPC\61\2-8.DOC unacceptable. The Group recalled that, in the evaluation of the Ecochlor ®
BWMS at Basic Approval, the local risks for aquatic organisms had been anticipated as a potential problem. Based on these concentrations, the Group is not able to recommend Final Approval for the Ecochlor ®
BWMS as presented.

Response: Discussion on the applicability of TRO as Cl 2 for chlorine

dioxide ' s degradation products is presented in

section 2.2. Ecochlor ®

would like to note that the highest discharge concentration reported in the prior Final Approval dossier for chlorite ion 24 hours (1 Day) after ballast water treatment is 3.6 mg/L, rather than 3.8 mg/L (Table T2.8a; MEPC 59/2/9).

Local risks for the aquatic environment anticipated by the Group at Basic Approval was based on a preliminary risk assessment using the information available at that

time. The full environmental risk assessment as documented in the prior Final Approval dossier as well as the whole effluent toxicity (WET) testing performed with the treated ballast water discharge did not support

those initial concerns. The environmental risk

assessment is further elaborated in section 3 below.

.8 Based on additional calculations using chlorite as representative, the Group concluded that the systems proposed discharge concentrations would lead to concentrations in the environment that would not exclude unacceptable risks to the aquatic organisms in the receiving waters.

Response: Discussion for MAMPEC modelling calculations is presented in section 3.

.9 The Group noted that the results of the Whole Effluent Tests (WET) clearly indicated that even with a 5-day tank holding time, the discharged water has both acute and chronic toxicity, so that more mitigation would be

needed for this BWMS.

Response: This comment is addressed in section 4.

.10 As the BWMS requires the storage of chemicals on board ship, the Group recognized that there will be a potential risk associated with storage safety problems. The submission states that as the chemicals used are ship's stores, then the provisions of the IMDG Code are not applicable. The Group recognized that this is the case, however strongly recommended that the provisions of the IMDG Code are follow ed as far as is practical and that the guidance provided in the IMO "Guidance to ensure safe handling and storage of chemicals and preparations used to treat ballast water and the development of safety procedures for risks to the ship and crew resulting from the treatment process" is also fully taken into account.

Response: Ecochlor ®

agrees with this statement and the concerns of the Group. As recognized by the Group, the provisions of the IMDG Code are not applicable to the

chemicals stored on board as consumables for use withMEPC 61/2/8 Annex, page 6

I:\MEPC\61\2-8.doc the Ecochlor ®

BWMS. The pre-installation review process, along with Ecochlor ' s ® existing system mitigation measures, crew and technician training, and active maintenance of the BWMS, support the

recommendations in IMO ' s guidance document for safe storage and handling of chemicals used to treat ballast water (BWM.2/Circ.20, July 2009). Section 5.3 elaborates

further.

.11 The Group recognized that the system utilizes an Active Substance with potential safety and environmental concerns and the Group has reviewed

the hazards and risks associated with the Active Substance.

No response required.

.12 The Group recognized that the applicant has provided some information on system controls and safety considerations for installation of the BWMS on board ship, together with provisions for maintenance and chemical replenishments to the system which w ill be performed by the manufacturer. The Group considered that the applicant did not provide sufficient information to permit a full evaluation of these safety matters, particularly with regard to procedures and risk mitigation measures applying to BWMS maintenance or chemical replenishment operations on board the ship.

Response: With respect, Ecochlor ®

is unclear what additional information is necessary, as the above comment appears to be in direct contrast to comment 0.14 below,

as well as comments in sections 3.1.5 and 4.2 of the review report (MEPC 60/2/11, annex 5), which indicate such issues were satisfactorily addressed.

Further, the Group ' s review of the Basic Approval dossier (MEPC 58/2/8, annex 5, section 4.10) stated,

" ... the Group considered that the unit operations where potential human exposure risks exist, e.g., maintenance and refilling operations, are limited in duration and frequency and risk mitigation measures were satisfactorily addressed by the applicant " . As such, no further information was provided in the prior Final Approval dossier (MEPC 59/2/9).

However, in a desire to provide additional information to the Group, Ecochlor ®

has included an example of a Health and Safety Plan (HASP) within the confidential appendices. The HASP is the general guiding document

for Ecochlor ®

technicians and/or representatives with respect to safety issues. This guidance, along with vessel-specific safety considerations that may be necessary to address relevant issues associated with a particular system, are followed by Ecochlor ®
technicians and/or representatives during system maintenance and chemical replenishment operations. An example of HASP has been provided in appendix 3

for consideration.MEPC 61/2/8 Annex, page 7

I:\MEPC\61\2-8.DOC .13 The Group noted that while additional corrosion tests had been conducted, they were insufficient and additional testing was recommended by the applicant's corrosion testing laboratory. The Group concurred and recommended that additional testing should be conducted in accordance with the guidance provided in section 5.1 of MEPC 59/2/16.

Response: Ecochlor ®

conducted corrosion testing according to the Group ' s recommendations for the review of the Basic Approval dossier (MEPC 58/2/8, annex 5) (see further discussion in section 5.1).

.14 The Group noted the human health assessment provided by the applicant and the Group accepted the view of the applicant that there should be no unacceptable risks to human health posed by the use of this BWMS if operated correctly.

No response required.

.15 In conclusion, having reviewed all the information provided by the applicant, the Group could not recommend to the MEPC that Final Approval be granted to the Ecochlor ®

BWMS.

Response: In summary, the following is suggested:

- reconsideration of the " TRO as Cl 2 " technique for chlorine dioxide, chlorite and chlorate;

- accept the new MAMPEC results which have been carried out per the GESAMP-BWWG harbour parameters;

- accept the proposed MADC for ClO 2 (section 3.4); and

- consider the corrosion and ballast tank coating study that was performed based on the GESAMP-BWWG recommendations from Basic Approval (MEPC 58/2/8, section 5.4).

In addition to the comments noted above, Ecochlor ®

also provides additional responses to specific sections within the Group's report.

.16 In Table 1 on page 4 (MEPC 60/2/11, annex 5), there is a word omitted in the "Applicants Response" column for the response to the Group's question for Basic Approval (section 0.3.1). The sentence should read "Information from the applicant has been added in response to the GESAMP-BWWG comment indicating that chlorite ion is not considered an Active Substance" (omitted word added with emphasis). The classification of chlorite ion as a Relevant Chemical is accurately reflected in section 3.3.3 of the Group's report.

.17 On page 14, the Group's reaction to the response to Question 4 indicates it is unclear how the shut-down pr ocedures will be used for manually controlled systems. Ecochlor ®

would like to clarify that the Ecochlor ®
BWMS is not operated manually and the response did not intend to indicate

such. What Ecochlor ®

does note in the prior Final Approval dossier is that some ships are equipped with more manual ballast water systems whereMEPC 61/2/8 Annex, page 8

I:\MEPC\61\2-8.doc valves within the ballast piping migh t be controlled manually. For example, this differs from other ships where the ballast system is controlled electronically and a crew member does not manually adjust valve positions. It is important to note that a distinction exists between the ships ballast water system and the Ecochlor ®

ballast water management system. How a ship controls its ballasting system and how the Ecochlor ®

system is programmed to operate automatically are separate matters. A ship that controls its ballast piping system (i.e. valve positions, pumps) in a more manual way does not preclude automatic operation of the Ecochlor ®
BWMS. Therefore, regardless of whether the ship is conducting complete ballasting, or topping off tanks, the Ecochlor ®

BWMS (including the flushing aspect of the shut-down procedure) will occur automatically without additional action from ship's crew.

.18 In section 3.3.8 of the report, the acronym MRL is stated as "Minimal Risk

Level". In Ecochlor's ® application MRL is defined as "Minimum Reporting

Limit".

2 CHEMISTRY

Detailed information about the chlorine dioxide chemistry associated with the Ecochlor ®
BWMS was presented in both the Basic Approval dossier (MEPC 58/2/2) and the earlier dossier for Final Approval (MEPC 59/2/9). Ther efore, this re-submission for Procedure (G9) Final Approval should be considered in conjunction with both prior dossiers. The following chemistry discussion is provided for additiona l clarification to address comments from the Group, as well as to highlight important information that was presented (Bubnis, 2010a) at the Chlorine/Chloride Based Ballast Water Treatment Workshop hosted by the North Sea Ballast Water Project and the German Federal Maritime and Hydrographic Agency

on 4 March 2010.

2.1 Overview of chlorine-based and chlorine-dioxide-based chemistry

There are numerous chlorine-based technologies that have received IMO Procedure (G9) Final Approval with more under review. Clearly, the Group has a high level of familiarity of chlorine chemistry. However, understanding the differences between chlorine-based and chlorine-dioxide-based chemistries is critical to a proper determination of environmental risk. Electro-chlorination of seawater/brine solution is the most widely used technique for ballast water treatment and generates chlorine through electrolysis of seawater or a chloride solution (Reaction 1). More specifically, the reaction can be defined through the anode (Reaction 2) to generate chlorine and the cathode (Reaction 3) to generate hydrogen.

See below:

Reaction 1 2Cl - + 2H 2 O + e - → 2OH - + Cl 2 + H 2 Reaction 2 Anode: 2Cl - → Cl 2 + 2e Reaction 3 Cathode: 2H + + 2OH - + 2e - → H 2 + 2OH -MEPC 61/2/8 Annex, page 9

I:\MEPC\61\2-8.DOC In water, chlorine will form hypochlorous acid (Reaction 4) and subsequent pH dependent equilibrium will be established between hypochlorous acid and hypochlorite ion (Reaction 5). At a pH of 7, there will be near equal amount s of hypochlorous acid and hypochlorite ion.

See below:

Reaction 4 Cl 2 + H 2 O ↔ HOCl + H + + Cl -
Reaction 5 HOCl ↔ OCl - + H +

The chart below shows the relationship between pH and the chlorine species present.

Chlorine Species

0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0

0 2 4 6 8 10 12 14

pH% Abundance

OClCl2 HOCl

Figure 1: Chlorine species at various pH values

Chlorine dioxide is a completely different chemistry with unique characteristics. With the

Ecochlor ®

BWMS, chlorine dioxide is generated on board ship as a dissolved gas in solution through the controlled mixing of Purate ® and sulfuric acid (Reaction 6). Chlorine dioxide is maintained as a dissolved gas in the treated ballast water. Chlorine dioxide treatment of water does not cause the formation of multiple chlorinated and oxidant chemical species. As indicated in Reaction 6, chlorine dioxide will not form chlorine or its dissociation compounds when added to fresh water, brackish water or seawater (Reaction 6).

See below:

Reaction 6 2 NaClO 3 + H 2 O 2 + H 2 SO 4 → 2 ClO 2 + 2 NaHSO 4 + 2 H 2 O + O 2

2.1.1 Bromide ion interaction and decomposition chemistry

It is well understood that the addition of chlorine into bromide ion containing waters will form bromine (Reaction 7). Similar to chlorine chemistry, bromine added to water will form hypobromous acid (Reaction 8) and then a pH-dependent equilibrium will be established between hypobromous acid and hypobromite ion (Reac tion 9). This is in contrast to chlorine dioxide, which does not react with bromide ion to form brominated oxidant species.

See below:

Reaction 7 Cl 2 + 2Br - + 2H + → Br 2 + 2HCl

Reaction 8 Br 2 ↔ HOBr + H + + Br Reaction 9 HOBr ↔ OBr - + H + Source: NovaChem Laboratories, USAMEPC 61/2/8 Annex, page 10

I:\MEPC\61\2-8.doc The chart below shows the relationship between pH and the bromine species present.

Bromine Species

0.0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0

0 2 4 6 8 10 12 14

pH% Abundance

OBr

Br2 HOBr

Source: NovaChem Laboratories,

US A

Figure 2: Bromine species at various pH values

In order to accurately identify relevant substances, it is also important to understand the decomposition products of chlorine/bromine and compare that to chlorine dioxide. The decomposition of chlorine chemistry will form chlorate ion and chloride ion (Reaction 10) while bromine chemistry will form bromate i on and bromide ion (Reaction 11). See below:

Reaction 10 2HOCl + OCl- → ClO3- + 2H+ + 2ClReaction 11 2HOBr + OBr- → BrO3- + 2H+ + 2BrThe decomposition of chlorine dioxide will form ch lorite ion (ClO2-) and chlorate ion (ClO3-) (Reaction 12) and ultimately chloride (Reaction 13). There is no formation of bromate ion.

See below:

Reaction 12 ClO 2 + e - → ClO 2 -
Reaction 13 2ClO 2 + 2OH - → H 2 O + ClO 3 - + ClO 2 -
Reaction 14 ClO 2 - + 4H + → Cl - + 2H 2 OMEPC 61/2/8 Annex, page 11

I:\MEPC\61\2-8.DOC 

### The chart below shows the relati onship between pH and the chlorine dioxide chemical species

present.

Figure 3: Chlorine dioxide species at various pH values

The lack of bromate formation with chlorine dioxide treatment has been confirmed through data obtained during shipboard testing as well as during land-based testing at NIOZ. As an example from the prior application for Final Approval (MEPC 59/2/9, Table T2.8), shipboard testing on the M.V. Moku Pahu clearly showed that the treatment of ballast water with chlorine dioxide in the presence of bromide (50 mg/L) did not result in formation of bromate. Table T2.8a (MEPC 59/2/9) can be referenced for land-based data, which also shows no

detection of bromate ion.MEPC 61/2/8 Annex, page 12

I:\MEPC\61\2-8.doc Table 1: Chemical analysis of ballast water treated on board the M.V. Moku Pahu

, San Francisco Bay Area (Richmond, CA)

Parameter Control Ballast

Water Ballast Water

Treated

Onboard + 3 Day

13 Feb 2008 Ballast Water

Treated

Onboard + 5 Day

15 Feb 2008 pH 7.6 7.3 7.3 FAC <0.05 mg/L <0.05 mg/L --

ClO 2 -- <0.05 mg/L <0.05 mg/L

ClO 2 - <0.05 mg/L 0.91 mg/L 0.24 mg/L

ClO 3 - <0.10 mg/L 0.49 mg/L 0.49 mg/L

Br - 50 mg/L -- --

BrO 3 - <0.02 mg/L -- <0.02 mg/L (+11 Day)

SO 4 - 2 1902 mg/L -- 1826 mg/L (+ Day 8)

THM ' s Bromodichloromethane

Bromoform

Chloroform

Dibromochloromethane <1 μg/L <1 μg/L <1 μg/L <1 μg/L -- <1 μg/L <1 μg/L <1 μg/L <1 μg/L

HAA ' s Dibromoacetic Acid

Dichloroacetic Acid

Monobromoacetic Acid

Monochloroacetic Acid

Trichloroacetic Acid <1 μg/L <1 μg/L <1 μg/L <1 μg/L <1 μg/L -- 12 μg/L <1 μg/L <1 μg/L <1 μg/L <1 μg/L

Analysis performed by NovaChem Laboratories

"

-- " = not measured

In summary, chlorine will form hypochlor ous acid (HOCl), hypochlorite ion (OCl
- ), chlorate ion (ClO 3 - ) and bromine will form hypobromou s acid (HOBr), hypobromite ion (OBr
- ), and bromate ion (BrO 3 - ). Chlorine dioxide (ClO 2 ) will form chlorite ion (ClO 2 - ), and chlorate ion (ClO 3 - ).

2.1.2 Disinfection by-product formation

Another significant difference between chlorine and chlorine dioxide chemistries is the formation of disinfection by-products (DBPs). The formation of by-products consisting of THMs (trihalomethanes) and HAAs (haloacetic acids) occurs when chlorine and/or bromine is added to water containing organic matter. This is because chlorine reacts by both oxidative and chlorination pathways.

Conversely, chlorine dioxide does not "chlor inate"; the mechanism for disinfection is oxidation. Oxidation by chlorine dioxide will not form chlorinated by-products such as THMs and formation of HAAs is significantly lower than that with chlorination. Ecochlor's ® data from shipboard and land-based testing, as presented in the prior Final Approval dossier (MEPC 59/2/9, Tables T2.8b and T2.8c), demonstrates this important feature of water

treatment with chlorine dioxide. The data cl early shows no formation of THMs and limited formation of one HAA (dibromoacetic acid, DBAA) when chlorine dioxide is used to treat water containing organic matter. As reflected in published chlorine-based BWMS dossiers, and as Table 2 below demonstrates, THM and HAA concentrations from the Ecochlor ®
BWMS are in sharp contrast compared to chlorine/bromine treatment chemistries.MEPC 61/2/8 Annex, page 13

I:\MEPC\61\2-8.DOC Table 2: Comparison of DBP concentrations for chlorine and

chlorine dioxide treatments

Parameter Chlorine

Based 1 (μg/L) Chlorine Dioxide

Based 2 (μg/L)

BDCM <1

Bromoform <1

Chloroform <1

DBCM <1

THM (Total) 260-410 <1

DBAA 12 - 36

DCAA <1

MBAA <1

MCAA <1

TCAA <1

HAA (Total) 48.5 – 100 12 - 36

1 Data presented by T. Bowmer at the IMO-WMU Global R&D Forum on Emerging Ballast Water Management Systems (Malmö, Sweden, January 2010)

2 Combined data from Ecochlor ® shipboard and land-based testing

While it is acknowledged that each DBP indentified as a Relevant Chemical during the application of a BWMS is subjected to an individual assessment of environmental and human health risks, these risk assessments presently have considerable uncertainties. This is due to the limited data available for some of the DBP substances with respect to both aquatic ecotoxicity (especially chronic effects), and ma mmal toxicity (especially carcinogenicity and reproductive and developmental toxicity). Limi ted DBP formation, as observed with the

Ecochlor ® system, therefore limits such uncerta inties of the risk assessment.

2.1.3 Hypochlorite ion and chlorite ion

There is often confusion between hypochlorite ion (OCl
- ) and chlorite ion (ClO 2 - ). Although sounding and appearing similar, hypochlorite ion (OCl
- ) is dramatically different from chlorite ion (ClO 2 - ). Ecochlor ®

provides Table 3 below to allow for a direct comparison between hypochlorite ion and chlorite ion. As noted above, the chlorine dioxide chemistry used with

the Ecochlor ®

BWMS does not produce hypochlorite ion.

Hypochlorite ion is an active ingredient formed when chlorine is added to water (section 2.1) and will: form bromine when added to bromide containing waters (section 2.1.1); be measured through the standard DPD test (section 2.2.1); form organic byproducts like THMs and HAAs in waters with organics; and will decompose to form bromate (section 2.1.2).

Conversely, chlorite ion is a Relevant C hemical formed through reaction of the active ingredient, chlorine dioxide. Chlorite ion does not: form bromine when added to bromide containing waters (section 2.1.1); is not measured by the standard DPD test (section 2.2.1) but rather through ion chromatography (section 2.2.2); will not form THMs or HAAs (chlorine dioxide does not form THMs and forms HAAs to a significantly less degree than hypochlorite ion) (section 2.1.2); chlorite ion will decompose to form chloride ion. See below:

OCl - ≠ ClO 2 - (Hypochlorite ion) (Chlorite ion)MEPC 61/2/8 Annex, page 14

I:\MEPC\61\2-8.doc Table 3: Comparison of hypochlorite ion and chlorite ion

Hypochlorite Ion Chlorite Ion CAS # (of the sodium salts) 7681-52-9 7758-19-2

Molecular Formula OCl - ClO 2 -

Chlorine Oxidation State +1 +3

Associated With Chlorine Chlorine Dioxide

In Water Chlorine Equilibrium pKa = 7.5

Cl 2 ↔ HOCl + Cl HOCl ↔ OCl - + Cl Ion pKa = 1.9

ClO 2 → ClO 2 -

pH Dependence YES NO

Reaction Mechanism Oxidation – very fast

Chlorination Organics → chlorinated organics Oxidation – very slow

End Product After Complete Reaction Typically Cl - Typically Cl Chloramine Formation YES NO

Reacts with Bromide Ion YES Hypobromite formation NO

2.2 Oxidant measurements

2.2.1 TRO as chlorine and DPD test method

As discussed above in section 2.1, when chlo rine is used to treat water, instantaneous dissociation into hypochlorous acid (HOCl) and hypochlorite ion (OCl
- ) takes place. As shown in Figure 1 above, these chemical species will be present at nearly equal concentration at neutral pH. When chlorinating seawater, the presence of bromide ions also causes the formation of hypobromous acid (HOBr) and hypobromite ion (OBr
- ). Chlorination of water can also result in the formation of additional oxidants that can include, but are not limited to, chloramines and bromamines. Therefore, water that has been treated with chlorine contains a complex mixture of chemical oxidants. Due to the difficulty in measuring each chemical species individually, the method of measuring Total Residual Oxidants (TRO) in a complex water sample is utilized. TRO is used to describe the aggregate concentration of oxidants present in a complex water sample, and is frequently quantified by utilizing the DPD (N,N'-diethyl- p- phenylenediamine) colorimetric test (equivalent method to EPA 330.5 or APHA SM4500-D). Therefore, TRO is a "surr ogate" measurement that provides a bulk concentration of various oxidant species present in complex water samples, but does not indicate the concentration of each chemical species individually.

Occasionally, terms other than TRO are used for the test results from the standard DPD test. These include Free Available Chlorine (FAC) and Free Available Bromine (FAB), depending on the oxidant species present. However, for this discussion, TRO is considered to mean the total of FAC and FAB (TRO = FAC + FAB), and the sum of the chlorine and bromine species measured by the DPD test. Of importance, is that the TRO methods frequently state that the measurement is calculated as mg Cl 2 /L, or "TRO as Cl 2 ".

A TRO measurement will detect the various chlorine and bromine oxidant species such as chlorine (Cl 2 ), hypochlorous acid (HOCl), hypochlorite ion (OCl
- ), bromine (Br 2 ), hypobromous acid (HOBr) and hypobromite ion (OBr
- ). However, the standard DPD test, at the neutral pH of fresh water and seawater, will not measure chlorine dioxide (ClO 2 ) or the various decomposition products discussed in section 2.1.1 (chlorite ion, chlorate ion andMEPC 61/2/8 Annex, page 15

I:\MEPC\61\2-8.DOC bromate ion) (Bubnis, 2010b). Therefore, although TRO implies that all residual oxidants are being measured, the standard DPD test has significant limitations and cannot be applied to all oxidative chemistries equally.

This can be clearly seen in Table 1 above (Table T2.8 in MEPC 59/2/9). In the samples evaluated the standard DPD test showed a non-detect reading (FAC = <0.05 mg/L) while through other specific test methods (discussed in section 2.2.2 below) measurable quantities of chlorite (ClO 2 - = 0.91 mg/L) and chlorate (ClO 3 - = 0.49 mg/L) were present. This finding is

consistent for Ecochlor's ® shipboard and all land-based testing (MEPC 59/2/9, Table T2.8a) where a TRO measurement (reported as FAC) was non-detect (less than detection limit), yet measurable quantities of chlorite ion and chlorate ion were present.

2.2.2 Methods for measuring chlorine dioxide, chlorite ion, chlorate ion and bromate ion

From section 2.2.1, it was found that the DPD test has limitations. The DPD test can be correctly used to quantify the primary active ingredients in chlorination/bromination chemistries but it clearly does not measure al l possible oxidants present in a water sample. For chlorine and bromine chemistry, the standard DPD test does not measure the Relevant Chemicals chlorate ion and bromate ion. For chlorine dioxide chemistry, the standard DPD test does not accurately measure the active ingr edient (chlorine dioxide) or the two Relevant Chemicals (chlorite ion and chlorate ion) (Bubnis, 2010b). Therefore, other selective and accurate test methodologies must be employed to measure these substances.

The preferred field test to measure chlorine dioxide is the Lissamine Green B (LGB) method (US EPA 327). This test is specific to chlo rine dioxide and eliminates the potential for interferences and false positives that are possible when attempting to utilize the DPD method to measure TRO in seawater treated with chlorine dioxide. As well, the concentration of chlorine dioxide using the LGB method can be easily measured in the field through a hand-held digital instrument.

There is no accurate and accepted field test for chlorite ion, chlorate ion, and/or bromate ion. As such, ion chromatography is the preferred method (US EPA 300.1 for chlorite and chlorate ions; US EPA 300.1/317 for bromate i on) (Bubnis, 2010b). These are laboratory run tests where proper sample preservation, storage and transportation is required for meaningful and defendable results. The methods are selective for these chemical species

and are accurate.

In contrast to chlorine/bromine chemistry where the surrogate method of TRO as Cl 2 is useful to quantify a majority of the oxidant species present, there are specific and accurate methods for measuring chlorine dioxide, chlorite ion, chlorate ion, and bromate ion (Bubnis, 2010b). As such, there is no scientific basis for applying a less specific surrogate method such as TRO. Additionally, because no chlorine is produced in the chlorine dioxide generation

method used with the Ecochlor ®

system, reporting the oxidant levels as "TRO as Cl 2 " is not accurate. There is no chlorine present.

2.3 Oxidant demand

As presented in prior dossiers (MEPC 58/2/2 and MEPC 59/2/9), when used to treat ballast water, chlorine dioxide will rapidly react (oxidize/disinfect) with susceptible organisms and certain chemical components over time. This c ontinuing consumption of chlorine dioxide is described as the chlorine dioxide demand. In practice, when chlorine dioxide is added to ballast water, there is a rapid decrease in the chlorine dioxide concentration followed by a continuing reaction of the remaining chlorine dioxide until the demand of the water is met. After meeting the demand, the chlorine dioxide will maintain a residual concentration andMEPC 61/2/8 Annex, page 16

I:\MEPC\61\2-8.doc continue to react with components in the ballast water. This results in a slower decrease in

concentration over time until the concentration of chlorine dioxide falls to a level that is undetectable by available analytical methods. Mu ch like chlorine dioxide, the chlorite ion

formed as chlorine dioxide reacts will also decrease due to oxidant demand. Detailed graphs and data for chlorine dioxide (F2.1 and T2.2) and chlorite demand (F2.4 and T2.5) under varying conditions were presented in MEPC 59/2/9. Examples of these are also presented below for ease of reference (chlorine dioxide – Table 4, Figure 4; chlorite – Table 5, Figure 5).

Table 4: Ecochlor ®

chlorine dioxide demand study, 4oC

Ecochlor ® Ballast Water Chlorine Dioxide Decay Study

Source Water New Jersey Ballast Water ClO2 Dose 5.06 mg/L Water Temp 4oC

Time after

ClO 2 treatment (minutes) Chlorine

Dioxide

ClO 2 (mg/L) Chlorite Ion

ClO 2 - (mg/L) Chlorate Ion

ClO 3 - (mg/L)

0 5.06 ND ND

5 3.50 0.742 0.001

30 2.80 0.855 0.055

60 1.90 1.285 0.110

180 1.40 1.727 0.169

300 1.10 -- --

480 0.21 -- --

660 0.00 1.796 0.282

0.00 1.00 2.00 3.00 4.00 5.00 6.00

0 200 400 600 800Concentration (mg/L)

Time (min) NJ Ballast Water Chlorine Dioxide Demand 5.06 mg/L, 4oC

Chlorine Dioxide

Chlorite Ion

Chlorate Ion

Source: Nova Chem Laboratories, USA

Figure 4: Example of chlorine dioxide demand curve, 4oCMEPC 61/2/8 Annex, page 17

I:\MEPC\61\2-8.DOC Table 5: Ecochlor ®

Chlorite ion demand study, 20oC

Ecochlor ® Ballast Water Chlorite Ion Demand Study

Source Water New Jersey Ballast Water Chlorite Dose 1.94 mg/L Water Temp 20oC

Time after ClO 2 - treatment (hour) Chlorite Ion

ClO 2 - (mg/L)

0 1.94

1 0.88

18 0.30

42 0.36

69 0.19

Ballast Water Chlorite Ion Demand
1.94 mg/L, 20 C

0.00 0.50 1.00 1.50 2.00 2.50

0 10 20 30 40 50 60 70 80

Time (Hr)Concentration (mg/L)

Figure 5: Example of chlorite ion demand curve, 20oC

The concept of oxidant demand has significance in the discussion of the data Ecochlor ®

has gathered during shipboard and land-based testing.

2.3.1 Comparison of oxidant demand for shipboard and land-based testing

In the prior Final Approval dossier (MEPC 59/2/9), Ecochlor ®

reported that the concentration of chlorine dioxide and its degradation products measured during land-based testing were higher than reported in the Basic Approval dossier (MEPC 58/2/2). This observation can be explained with the concept of oxidant demand. To ensure proper inactivation of potential aquatic invasive species, chlorine dioxide is dosed at a concentration high enough to maintain a residual that will act on the biofilm and sediment that will be present in actual ballast tanks. These contribute significantly to the demand for chlorine dioxide within the ballast tank(s). In direct contrast to an actual ballast tank, the controlled environment of land-based testing consisted of very clean tanks. As standard protocol, the land-based tanks were washed with high-pressure hoses before each test cycle, allowing no biofilm or

sediment to accumulate in the test tanks. Without these biofilms and/or sediments that are normally present in ballast tanks, the typica l timeline for chlorine dioxide and chlorite ion decay were not observed.MEPC 61/2/8 Annex, page 18

I:\MEPC\61\2-8.doc Land-based testing conditions were also static and no mixing of the treated water occurred as it would on board ship. This was a contributing factor in the observed differences in chlorine dioxide and chlorite ion concentrations noted during land-based testing compared to an onboard treatment scenario. In the static water of land-based testing, once the oxidant demand of the water was met, chlorine dioxide and chlorite ion concentrations became relatively stable and decay required more time. This is directly related to the differences in shipboard and land-based testing conditions, and the differing oxidant demand in each case. This is reflected in Table T2.8a in document MEPC 59/2/9, which has been modified to highlight only chlorine dioxide and chlorite in treated water samples at Days 0, 1 and 5 for two test cycles (Table 6).

Table 6: Summary of chlorine dioxide and chlorite concentrations, land-based testing

Treated Ballast

Water 5 mg/L ClO 2 Days After

Treatment Sample ID ClO 2 a (mg/L) Chlorite b
(mg/L)

Seawater (average salinity

31.9 ± 1.3 PSU c ) 0 5HS 12 June 08 - TX >2.5 3.83

1 5HS 13 June 08 - TX 0.85 3.11

5 5HS 17 June 08 - TX ND 2.26

Brackish Water (average salinity

23.1 ± 0.65 PSU c ) 0 3LS 26 June 08 - TX >2.5 3.18

1 3LS 27 June 08 - TX 0.67 3.12

5 3LS 1 July 08 - TX ND 2.8

a Chlorine dioxide residual measured using the LGB method (Palintest Ch lorDiox Duo instrument)

b Analysis performed by NovaChem Labs, USA

The land-based testing data above indicate that chlorine dioxide and chlorite decay over time, but not as rapidly as has been observed on board ship. The difference in oxidant demand is evident when chlorine dioxide and chlorite concentrations from land-based testing and shipboard ballast water samples are compared. Chlorite levels from shipboard data are consistently lower than chlorite concentrations measured in land-based testing performed at NIOZ. Residual chlorine dioxide follows the same trend with higher residual concentrations measured in land-based testing water samples. Table 7 below provides data from two separate shipboard studies.

Table 7: Summary of chlorine dioxide and chlorite concentrations, shipboard testing

Test

Substance Days After

Treatment Sample ID ClO 2 a (mg/L) Chlorite b
(mg/L)

Shipboard

Studies

Treated

Ballast Water 5 mg/L ClO 2 0 Forepeak tank 0.26 NM 3 Forepeak tank ND 0.91 5 Forepeak tank ND 0.24

1 AC- Tank 2 ND 0.34

2 AC- Tank 2 ND 1.12

3 AC- Tank 2 ND 0.64

4 AC- Tank 2 ND 0.53

5 AC- Tank 2 ND 0.41

a Chlorine dioxide residual measured using the LGB method (Palintest Ch lorDiox Duo instrument)

b Analysis performed by NovaChem Labs, USAMEPC 61/2/8 Annex, page 19

I:\MEPC\61\2-8.DOC When comparing the data, the Day 0 samples from NIOZ indicate >2.5 mg/L ClO 2 (Table 6) while on board ship only 0.26 mg/L ClO 2 was measured at Day 0 (Table 7). Similarly, 3.11 mg/L ClO 2 - was measured in the land-based sample on Day 1, while 0.34 mg/L ClO 2 - was reported for the shipboard study. During another shipboard study the following ClO 2 decay was observed and the data is presented in Table 8 and Figure 6 below.

Table 8: Chlorine dioxide decay study, shipboard testing

Ecochlor ® Ballast Water Chlorine Dioxide Decay

Source Water New Jersey Ballast Water

ClO 2 Dose 5 mg/L Water Temp 24oC

Time after ClO 2 treatment (mins) Chlorine Dioxide Residual

ClO 2 (mg/L)

0 1.77

45 1.67

91 1.75

171 0.92

245 0.67

576 0.19

650 ND

Figure 6: Chlorine dioxide decay study, shipboard testing

The residual chlorine dioxide concentrations, as well as the concentrations of the Relevant Chemical chlorite ion, that were reported from land-based testing are the highest values ever documented by Ecochlor ® . The concentrations of these substances observed during shipboard studies are representative of actual ballast tank conditions that are encountered during practical use of the Ecochlor ®

BWMS.MEPC 61/2/8 Annex, page 20

I:\MEPC\61\2-8.doc 3 HYDRODYNAMIC MODELLING AND ASSESSMENT OF ENVIRONMENTAL

RISK

As discussed in document MEPC 59/2/9 and in section 2.3.1 above, the concentrations of substances observed during land-based testing were higher than those that had been recorded during studies of the Ecochlor ®

system on board ship. However, as required by the Methodology for information gathering and the conduct work of the GESAMP-BWWG, the risk assessment undertaken for the prior Fina l Approval dossier was based on data from ballast water discharge samples drawn from the land-based test set-up. The discharge

concentrations were carried forward in hydrodynamic modelling to derive Predicted Environmental Concentration (PEC) values. These PEC values were then used to derive a ratio using the Predicted No Effect Concentration (PNEC) for each substance.

In section 3.1 below, Ecochlor ®

presents additional MAMPEC modelling results based on the parameters provided by the GESAMP-BWWG. Additional discharge concentrations and resulting PEC values for chlorine dioxide are presented to support a reduced chlorine dioxide

MADC.

3.1 Re-calculation of PEC values using the MAMPEC model

In section 6.3.12 of document MEPC 60/2/11, annex 5, Ecochlor ®

notes that the review of the Final Approval dossier included PEC value calculations for chlorite by the GESAMP-BWWG. The Group's result was greatly different (nearly 1000 times larger) than the chlorite PEC calculated by Deltares, who performed the modelling and PEC derivation, and which was subsequently used in Ecochlor's ® PEC/PNEC ratios. The modelling input parameters are absolutely critical to the outcome of the PEC and all modelling scenarios cannot be considered as equivalent. More specifically, the three input parameters that are the primary drivers of the PEC value are 1) substance "load", 2) amount of "flushing" in the harbour, and 3) the behaviour of the substance(s) being modelled.

The GESAMP-BWWG review report did not incl ude details on the input parameters used in recalculating the chlorite PEC. In an effort to understand the discrepancies in PEC value results, Ecochlor ®

commissioned Deltares to perform additional hydrodynamic modelling. To enable modelling in the same manner as done by the GESAMP-BWWG, the German Administration obtained the input parameters used for the MAMPEC model directly from the GESAMP-BWWG. The following harbour definition (Figure 7) and emission scenario (Figure 8) information was provided to Ecochlor ®

as the scenario used during the evaluation

of the Ecochlor ®

BWMS.

(Figure 7 provided in the confidential dossier.)

Figure 7: Harbour definition information provided by the GESAMP-BWWG

(Figure 8 provided in the confidential dossier.)

Figure 8: Emission parameter information provided by the GESAMP-BWWGMEPC 61/2/8 Annex, page 21

I:\MEPC\61\2-8.DOC The version of MAMPEC used by the GESAMP-BWWG was not specified. As such,

Ecochlor ®

was asked by the German Administration to proceed with re-modelling using the best assumptions. Based on expert guidance from Deltares, the last publicly released version of MAMPEC (version 2.5.04) was used.

The "compound definition" input parameters used in the MAMPEC model by the GESAMP-BWWG was not specified. Therefore, the compound definition parameters (e.g., decay rate) that Deltares used in the original MAMPEC modelling for Ecochlor ®

were utilized. The compound definition screen for ch lorite is provided as an example below (Figure 9). The compound definition screens for all new modelling scenarios are included behind the Deltares reports in appendix 1.

(Figure 9 provided in the confidential dossier.)

Figure 9: Example of compound definition parameters

Although the GESAMP-BWWG review report focused on the PEC value for chlorite,

Ecochlor ®

re-modelled all four substances associated with the Ecochlor ®

BWMS. Detailed information is provided below.

3.2 Details of the modelling parameters for PEC re-calculation by Ecochlor ®

To determine the substance emission (i.e. "loading") the same discharge concentrations as presented in the prior Final Approval dossier were used. That is, the highest 24-hour values

of ClO 2 , ClO 2 - , ClO 3 - and DBAA measured in treated ballast water discharge as shown in document MEPC 59/2/9, Tables T2.8a and T2.8c were re-modelled.

In addition, Ecochlor ®

re-calculated PEC values accord ing to the GESAMP-BWWG scenario

for three additional chlorine dioxide concentrations. The concentrations selected are 0.4 mg/L ClO 2 , 0.2 mg/L ClO 2 , and 0.1 mg/L ClO 2 . As part of the approval process in the United States, the Washington State Department of Ecology (DOE) has conducted an environmental risk assessment for the discharge of chlorine dioxide associated with the

Ecochlor ®

BWMS. Ecotoxicology studies were performed according to the DOE requirements and based on their findings, the maximum allowable discharge concentration (MADC) for chlorine dioxide is 0.4 mg/L. As such, Ecochlor chose to model the DOEs allowed MADC using MAMPEC to der ive a PEC value. Also, as Ecochlor ®

is proposing that the MADC of 0.2 mg/L ClO 2 will be verified as a mitigation measure (q.v. 3.4) to ensure the environmental acceptability of treated water discharge, this concentration was

modelled as well. An additional ClO 2 concentration of 0.1 mg/L was also modelled.MEPC 61/2/8 Annex, page 22

I:\MEPC\61\2-8.doc Based on the calculation shown in the GESAMP-BWWG provided emission screen in Figure 8 above, the substance emissions were calculated as follows:

Chlorine dioxide:

Emission = [chlorine dioxide, g/m 3 ] in BW * BW volume, m 3 /d Emission 1 = 0.85 g/m 3 chlorine dioxide * 200000 m 3 /d BW = 170,000 g/d Emission 2 = 0.4 g/m 3 chlorine dioxide * 200000 m 3 /d BW = 80,000 g/d Emission 3 = 0.2 g/m 3 chlorine dioxide * 200000 m 3 /d BW = 40,000 g/d Emission 4 = 0.1 g/m 3 chlorine dioxide * 200000 m 3 /d BW = 20,000 g/d

Chlorite:

Emission = [chlorite, g/m 3 ] in BW * BW volume, m 3 /d Emission = 3.6 g/m 3 chlorite * 200000 m 3 /d BW = 720,000 g/d

Chlorate:

Emission = [chlorate, g/m 3 ] in BW * BW volume, m 3 /d Emission = 1.47 g/m 3 chlorate * 200000 m 3 /d BW = 294,000 g/d

Dibromoacetic Acid (DBAA):

Emission = [DBAA, g/m 3 ] in BW * BW volume, m 3 /d Emission = 0.036 g/m 3 DBAA * 200000 m 3 /d BW = 7,200 g/d

Table 9 summarizes the emissions for each substance.

Table 9: Summary of treated ballast water substance emissions

Substance Discharge

Concentration [g/m 3 ] BW Discharge

Volume

(m 3 /d) Emission [g/d]

Chlorine dioxide (highest 24-hr concentration from land-based testing) 0.85 200000 170,000 Chlorine dioxide (WA State DOE Approved MADC) 0.4 200000 80,000 Chlorine dioxide (Proposed Procedure (G9) Approval MADC) 0.2 200000 40,000
Chlorine dioxide 0.1 200000 20,000
Chlorite 3.6 200000 720,000
Chlorate 1.47 200000 294,000
Dibromoacetic acid (D BAA) 0.036 200000 7,200

3.3 PEC re-calculation results and PEC/PNEC ratios

Using the MAMPEC scenario parameters prov ided by the GESAMP-BWWG, the MAMPEC software version suggested by Deltares, and Ecochlor's ® chemical input values (as presented in the prior Final Approval dossier) new PEC values were derived. The compound information, including the chemical decay rates (based on laboratory studies), used for PEC re-calculation are the same as used in Ecochlor's ® previous PEC calculations (MEPC 59/2/9, Tables T5.3 and T5.5 and section 5.3.3.2). Based on the new PEC values, new PEC/PNEC ratios were derived. The tables below summarize the results.MEPC 61/2/8 Annex, page 23

I:\MEPC\61\2-8.DOC Table 10: Re-calculated Predicted Environmental Concentrations – MAMPEC

Substance Discharge

Concentration (g/m 3 ) Mass Discharge

Rate In Model (g/s) 1 st Order Decay Rate (1/d) Half-life in Water (days) PEC (μg/L)

Chlorine Dioxide 0.85 1.967 145.4 4.75E-03 0.0218

Chlorine Dioxide 0.4 0.926 145.4 4.75E-03 0.0103

Chlorine Dioxide 0.2 0.463 145.4 4.75E-03 0.00513

Chlorine Dioxide 0.1 0.231 145.4 4.75E-03 0.00257

Chlorite 3.6 8.33 463.7 1.49E-03 0.0290

Chlorate 1.47 3.402 43.2 1.60E-02 0.127

Dibromoacetic acid 0.036 0.0833 0 ∞ 1.03

Table 11: Re-calculated PEC/PNEC ratios

Substance Lowest
Observed Effect

Concentration (mg/L) Assessment

Factor PNEC (μg/L) PEC / PNEC Ratio (μg/L)

Chlorine Dioxide (0.85 mg/L discharge concentration) 0.02 1000 0.02 0.0218/0.02 = 1.09

Chlorine Dioxide (0.4 mg/L WA State DOE MADC) 0.02 1000 0.02 0.0103/0.02 = 0.515

Chlorine Dioxide (0.2 mg/L proposed MADC) 0.02 1000 0.02 0.00513/0.02 = 0.267

Chlorine Dioxide (0.1 mg/L) 0.02 1000 0.02 0.00257/0.02 = 0.129

Chlorite 0.58 1000 0.58 0.0290/0.58 = 0.05

Chlorate 0.06 100 0.60 0.127/0.60 = 0.212

Dibromoacetic acid 69.0 1000 69.0 1.03/69.0 = 0.015

The PEC values and PEC/PNEC ratios obtained with Ecochlor's ® re-modelling effort (using the GESAMP-BWWG scenario) indicate that the new values are lower than presented in the prior Final Approval dossier. With respect to chlorite, the PEC result and PEC/PNEC ratio differ significantly from those presented in the GESAMP-BWWG report (MEPC 60/2/11, section 6.3.12).

It should also be noted that environmental risk for chlorine dioxide, chlorite and chlorate are evaluated individually in EU regulatory fram eworks (e.g., REACH and Biocidal Products Directive) (Thomas, 2010). That is, PNEC values are based on toxicity endpoints for each

individual substance and PEC values are based on measured and modelled concentrations of these compounds individually (Thomas, 2010) . This provides additional validity to Ecochlor's risk assessment for these substances, which is based on the existing risk assessment methodology for the individual substances, as well as whole effluent toxicity testing.

3.4 Maximum allowable discharge concentrations

Based on the additional modelling scenarios, the maximum ClO 2 residual of 0.85 mg/L from the land-based testing resulted in a PEC/PNEC ration of 1.09 using the GESAMP-BWWG harbour scenario. Based on the shipboard data presented above, Ecochlor ®

would like toMEPC 61/2/8 Annex, page 24

I:\MEPC\61\2-8.doc reiterate that a chlorine dioxide residual of 0.85 mg/L 24 hours post-treatment cannot be reasonably anticipated. In any case, Ecochlor ®

accepts that a lower discharge concentration

for ClO 2 is desirable. As such, Ecochlor ®

performed modelling for the proposed MADC of 0.2 mg/L. The PEC result allows for calculation of a PEC/PNEC ratio of 0.267, which is well below 1. As further mitigation, Ecochlor ®

has discussed with the German Administration that part of the Type Approval process will include verifying that the ClO 2 MADC of 0.2 mg/L (using the LGB method) is not exceeded prior to discharge of treated ballast water.

To ensure environmental acceptability of treated ballast water discharge and verify that the MADC of 0.2 mg/L ClO 2 is not exceeded a manual measurem ent of the chlorine dioxide residual will be taken prior to the initial discharge of a de-ballasting operation. As presented in the prior Final Approval dossier (section 2.5), chlorine dioxide residual in treated ballast water is measured using the Palintest Chlordiox-Duo instrument which employs the LGB method. The Chlordiox-Duo digital meter and the LGB method allows for easy calibration of the meter, simple addition of co lorimetric reagents and direct measurement of the chlorine dioxide concentration. To measure low concentrations, as will be applicable in treated ballast water, the LGB Low Range (LR) test method is used. This method has a range of 0.1 mg/L to 2.5 mg/L with a detection limit of 0.1 mg/L. The LGB test for chlorine dioxide will verify that the MADC of 0.2 mg/L ClO 2 is not exceeded. This information would be recorded on board the vessel and could be used for any port State control monitoring that might be required. Information regarding the Palintest and Ecochlor's ® standard operating procedure (SOP) for measuring chlorine dioxide is included in appendix 4.

With respect to chlorite and chlorate, the prior application for Final Approval indicated that the PEC/PNEC ratios for both substances were <1, even when using the highest discharge concentrations and worst-case modelling scenarios and PEC results. This result (PEC/PNEC ratio <1) was supported again when Ecochlor ®

utilized the

draft GESAMP-BWWG harbour scenario to determine the new PEC values. Based on section 7.3.2 of the Methodology, PEC/PNEC ratios <1 indicate that no further assessment of effects to the aquatic environment would be required.

Even though the PEC/PNEC ratio assessment clearly demonstrates that there is no unacceptable risk from the discharge of chlorite ion or chlorate ion, Ecochlor ®

has agreed with the German Administration (BSH) to monitor chlorite ion and chlorate ion levels from shipboard treated ballast water (through ion chromatography analysis). This data will allow BSH to verify discharge concentrations as part of the Type Approval oversight of the

Ecochlor ®

BWMS.

4 DISCHARGE ECOTOXICITY

As presented in the prior Final Approval dossier, whole effluent toxicity (WET) testing on discharge samples drawn from the land-based unit resulted in Pacific oyster ( Crassostrea gigas ) being the most sensitive species of six taxonomic groups tested. The average EC 50 for all C. gigas tests was 51% (average NOEC = 31%). Thus a two-fold dilution is necessary to reach a concentration less than the EC 50 value and a three-fold dilution is necessary to reach a concentration less than the NOEC value for C. gigas.MEPC 61/2/8 Annex, page 25

I:\MEPC\61\2-8.DOC Based on the guidance in section 4.2.4.2 of the EU Technical Guidance Document (TGD) on Risk Assessment (2003), a default dilution factor of 100 for discharges to coastal zones can be assumed and is representative of a realistic worst-case. This is based on the differing dilutions in various environments that can range fr om a factor of 10 (minimal tidal influence) to a factor of 500 (larger current/tidal influence) that have been estimated. Because releases of ballast water can occur in a wide range of situations, the generic local exposure assessment approach discussed in the TGD is appropriate for this assessment.

The 2- or 3-fold dilution that would be required to reach the EC 50 or NOEC value derived from WET testing of Ecochlor ®

ballast water discharges is far below the default worst case dilution factor of 100 utilized in the TGD guidance. Therefore, it can be reasonably assumed that the low level dilution of 2 or 3-fold will be achieved immediately upon discharge of treated ballast water. Further, this assessment indicates no unacceptable aquatic risk.

5 SHIP SAFETY AND MAINTENANCE

5.1 Corrosion and ballast tank coatings

In the application Ecochlor ®

submitted in December of 2008, Ecochlor ®

had already identified a suitable testing laboratory for the corrosion study and was awaiting representative samples of coated panels from leading ballast tank coat ing suppliers. This study was initiated based on the recommendations from GESAMP-BWWG in the review of the application for Basic Approval (MEPC 58/2/8, annex 5, sections 0.8 and 2.3). It was anticipated in December 2008 that the study would last three (3) months as requested by the Group. However, since the application for Final Approval was not reviewed in the first two GESAMP-BWWG meetings of 2009, Ecochlor ®

continued the study for 120 days which would allow completion of the study and report before the September 2009 review. Section 6.1.2.5 of the prior Final Approval do ssier (MEPC 59/2/9) stated that the study had

been initiated.

The study included bare metal samples and a total of four (4) different ballast tank coatings from two global paint suppliers (International Paint, PPG). The coupons and panels were partially submerged to evaluate the air/water interface in treated and untreated simulated seawater for periods of 2 months, 4 months and 6 months based on standard laboratory practices. Water samples were replenished every two weeks to simulate a frequent vessel ballasting schedule, which provided conservative results. The coupons and panels were analysed by independent laboratories including a metal analysis group, each of the two paint suppliers and a team of corrosion experts.

Although there are deviations from the GESAMP-BWWG recommendations in document MEPC 59/2/16, section 5.1, the study undertaken and the data gathered by Ecochlor ®

is comprehensive and demonstrates no corrosi on impacts can be reasonably expected. The primary deviations in the Ecochlor ®

study are related to 7 of the 12 suggested protocols. Seven of the test protocols are only performed when a surface defect is observed in the coating. As no surface defects were noted, these test protocols were not warranted as

summarized in Table 12 below.MEPC 61/2/8 Annex, page 26

I:\MEPC\61\2-8.doc Table 12: Summary of corrosion test methods

Analytical

Test Method Recommended by GESAMP-BWWG Test Not Warranted

ASTM G78 √

ASTM G61-86 √

ISO 2812-2 √

ASTM G31-72 √

ISO 11463 √ √

ASTM G46 √ √

ISO 4624 √

ISO 4628-2 √ √

ISO 4628-3 √ √

ISO 4628-4 √ √

ISO 4628-5 √ √

ISO 4628-8 √ √

Of the other five recommended tests, Ecochlor performed ISO 4624, an equivalent test to ASTM G31-72, and also ASTM G1. Ecochlor ®

respectfully requests that the GESAMP-BWWG appreciate that the corrosion study protocol and testing was initiated prior to the recommendations established at MEPC 59 (April 2009), which occurred four months after the prior application for Final Approval was submitted (December 2008). The study undertaken and the data gathered are comprehensive and appropriate to demonstrate no corrosion impacts to vessels. Because Ecochlor tested four separate ballast tank coatings, which is more than recommended in document MEPC 59/2/16, there is less uncertainty in the data and conclusions regarding corrosion risk to ballast tank coatings.

The corrosion study report was not submitted to the GESAMP-BWWG prior to review of the dossier based on document MEPC 59/2/13, section 2.3.10. This section states "If an Administration provides additional informati on regarding a proposal for approval that has been already submitted, a new position at the end of the waiting list will be assigned and the respective proposal will be evaluated according to the new chronological order". As such, there was concern about submitting the corrosion report prior to the GESAMP-BWWG meeting and it was envisaged that the GESAMP-B WWG would note the mention of the study (MEPC 59/2/9, section 6.1.2.5) and request the data. However, no questions concerning corrosion were asked during the review and there was no opportunity to submit the corrosion report.

Ecochlor's ® corrosion study is summarized in two reports: Laboratory Immersion Corrosion Testing of Ballast Panels in Chlorine Dioxide Treated Artificial Seawater (NovaChem Laboratories, 2009) and Corrosion Evaluation of Test Panels Exposed to ClO 2 Treated and
Untreated Seawater (Corrosion Testing Laboratories, Inc. 2009). The reports are included in appendix 2.

5.2 Fire risk mitigation

The GESAMP-BWWG indicated that it was partially satisfied with the information provided for fire mitigation. Ecochlor ®

appreciates that the Group understands that ship-specific measures will be identified on a case-by-case basis. However, due to the variation inMEPC 61/2/8 Annex, page 27

I:\MEPC\61\2-8.DOC matters such as vessel type, location where the BWMS may be installed on a particular vessel, the existing fire system(s) on board, and the cargo carried by the vessel, defining specific fire mitigation arrangements to be put in place for a hypothetical vessel is not feasible. Further, Ecochlor ®

is clearly responsible for provid ing the necessary information to identify any potential chemicals hazards associated with the BWMS system. However, as a BWMS vendor, it is beyond Ecochlor's ® scope to engineer or specify precise arrangements for fire mitigation on board a vessel.

It is important to note that an installation on board will be reviewed and approved by the ships' classification society, which has the ulti mate decision on what will be required for safe BWMS installation. If the classification society deems a measure necessary for safe installation, that is what must be implemented. If the vendor is unwilling to comply with the requirements of the classification society, then the system will not be approved for

installation.

As an example, a major classification society recently reviewed the Ecochlor ®

BWMS for installation on a specific vessel for construction in Japan. During that review, this classification society specified requirements in regard to fire mitigation. These include:

.1 portable fire extinguisher is to be installed adjacent to the Ecochlor ®

BWMS house; and

.2 cooling water spray to cover the outside of the Ecochlor ®

BWMS to be considered by means of an existing hydr ant with canvas hose or additional water spray nozzle like one for paint stores.

Requirements agreed to by shipyard and Ecochlor ®

include:

.1 powder foam or C0 2 as portable extinguisher shall be installed in the

Ecochlor ®

BWMS or around the entrance of the house; and

.2 installation of a fixed spray nozzle to cover the entire Ecochlor ®

BWMS shall be provided with water quantity of 5 litres/m 2 /minute.

5.3 Chemical storage

Sections 3.0.8, 6.1.3, 6.1.4, 6.1.5 and 6.2 of the prior Final Approval dossier (MEPC 59/2/9) presented discussion pertaining to safe chemical storage and handling, as well as the measures (such as PPE) that mitigate the risks. Further, preparing for BWMS installation on board a ship requires comprehensive reviews by Ecochlor's ® marine engineers, the vessel engineers, as well as the ships' classification society. Additional mitigation measures that may be deemed necessary by these competent parties to ensure safe BWMS installation on a specific ship will be implemented as needed.

As recognized by the Group, the provisions of the IMDG Code are not applicable to the storage of the chemicals associated with the Ecochlor ®

BWMS. However, the IMDG Code will be considered by Ecochlor ® , in consultation with the ship owner/master and/or classification society, as appropriate, in the following respects:

- chemical packing (e.g., labelling, materials of construction, and/or special provisions);

- emergency schedules for fire and spillage; and

- stowage and segregation.MEPC 61/2/8 Annex, page 28

I:\MEPC\61\2-8.doc Section 3.0.8.1 of the prior Final Approval dossier provided information about chemical storage tanks such as tank construction materials, capacity, containment, and prior approval by Lloyd's and ABS classification societies. The MSDS for each chemical stored on board (Purate ® and sulfuric acid) provided in appendix B of the prior Final Approval dossier indicates the container labelling requirement s, which are implemented by Ecochlor.

Section 3.0.9 of the prior Final Approval dossier includes information about fire mitigation measures. These include the flammability of the chemicals, fire avoidance measures (storage away from incompatible materials, etc.), and fire fighting methods. With respect to a fire situation, section 3.0.9 provides information similar to the guidance in the IMDG Code Emergency Schedules for fire (EmS F-H (Purate ® ) and EmS F-A (sulfuric acid) such as using water sprays to keep containers cool and prevent spread of fire.

Section 3.0.9.2 of the prior Final Approval dossier provides information on accidental release (i.e. chemical spillage) measures, which is similar to the guidance in the IMDG Code Emergency Schedules for spillage (EmS S-Q (Purate ® ) and EmS S-B (sulfuric acid). The measures outlined in section 3.0.9.2 include use of respiratory protection, proper PPE, ventilation, and use of inert, non-combustible sorbent materials.

The IMDG Code will also be consulted to ensure that Purate ® and sulfuric acid storage tanks will be placed on board with sufficient segregation from incompatible substances. Further, applicable safety measures will be included during the Type Approval process with the

German Administration.

The IMO's "Guidance to ensure safe handling and storage of chemicals and preparations used to treat ballast water and the development of safety procedures for risks to the ship crew resulting from the treatment process" (BWM.2/Circ.20, July 2009) will be taken into consideration. The recommendations in "Methodology for addressing risk, section 5" for the role of the BWMS supplier are specifically considered by Ecochlor ® , in consultation with the ship owner/master as appropriate, for each individual vessel as follows:

- clear operational instructions and training for the BWMS are provided to ships'

crew;

- MSDSs for Purate ® and sulfuric acid are provided;

- only Ecochlor ®

technicians or qualified repres entatives will conduct chemical re-supply operations (this will never be performed by ships' crew);

- Ecochlor ®

performs all routine maintenance of the BWMS and associated components (including chemical storage tanks);

- all risks associated with the chemical s are fully disclosed and discussed during

the Ecochlor ®

training program for ships' crew; and

- Ecochlor ®

is directly involved with ensuring that all necessary personal protective equipment and/or spill response kits that may be needed during an emergency situation related to the BWMS are on board the vessel. These aspects

are also included in the Ecochlor ®

training program for ships' crew.

The pre-installation review process, along with Ecochlor's ® existing system mitigation measures, crew and technician training, and active maintenance of the BWMS, support the guidance in the IMDG Code and the recommendations in IMO's guidance document for safe storage and handling of chemicals used to treat ballast water.MEPC 61/2/8 Annex, page 29

I:\MEPC\61\2-8.DOC 6 SUMMARY

The final recommendations made by the GESAMP-BWWG in section 7.4 (MEPC 60/2/11, annex 5) are summarized below. The sections in this re-submission where the comments are addressed are also listed, as follows:

7.4.2.1 The proposed MADCs for chlorine dioxide, chlorite ion and chlorate ion significantly exceed the discharge concentration of 0.1 mg/L to 0.2 mg/L TRO (as Cl 2 ) previously recommended by the Group.

In sections 2 and 3 Ecochlor ® discusses the applicability of TRO

measurements to chlorine dioxide chemistry and MADCs, respectively.

Ecochlor ®

is agreeable to an MADC of 0.2 mg/L for chlorine dioxide. However, chlorine dioxide measurements should be done using the more appropriate method of LGB, rather than TRO as Cl 2

.

7.4.2.2 To provide certainty for environmental safety, monitoring and control of the discharge should be incorporated to ensure that the finally agreed MADCs for all
Active Substances and Relevant Chemicals are not exceeded.

The LGB method can be used to monitor the concentration of chlorine dioxide in treated ballast water discharge to ensure the proposed MADC of 0.2 mg/L of ClO 2 is not exceeded (refer to the discussion in section 3.4).

7.4.2.3 The provisions of the IMDG Code should be followed as far as practical and the guidance provided in the IMO " Guidance to ensure safe handling and storage of chemicals and preparations used to treat ballast water and the development of safety procedures for risks to the ship and crew resulting from the treatment

process " should also be fully taken into account.

Ecochlor ®

agrees with the recommendations of the GESAMP-BWWG in this regard (refer to the response in section 5.3).

7.4.2.4 Further attention to procedures and risk mitigation measures applying to BWMS maintenance and chemical replenishment operations on board the ship.

Refer to the response in section 0.12. A sample health and safety plan has been provided in appendix 3 to assure the Group that these safety matters are fully considered by Ecochlor ®

.

7.4.2.5 Additional corrosion testing should be conducted in accordance with the guidance provided in document MEPC 59/2/16, section 5.1.

Ecochlor ®

conducted the corrosion testing that was recommended by the Group during Basic Approval prior to the above recommendation. The study followed similar analytical techniques and verifies no significant

difference between control and chlorine dioxide treated bare metal and ballast tank coating coupons (refer to the discussion in section 5.1, and appendix 2 for corrosion study reports).MEPC 61/2/8 Annex, page 30

I:\MEPC\61\2-8.doc 7.4.2.6 A more detailed description of arrangements to be put in place for fire mitigation measures.

The appropriate fire mitigation measures will be implemented by Ecochlor ®
(refer to the discussion in section 5.2).

7 REFERENCES

Bubnis, B. 2010a, Chemistry of Oxidants in Ballast Water Treatment. (Presented at the Workshop on Chlorine/Chloride Based Ballast Water Treatment, 4 March 2010, Hamburg, Germany).

Bubnis, B. 2010b, Total Residual Oxidant Measurements. (Presented at the Workshop on Chlorine/Chloride Based Ballast Water Treatment, 4 March 2010, Hamburg, Germany).

European Chemicals Bureau, 2003. Technical Guidance Document on Risk Assessment,

TGD Part II.

Thomas, P., 2010. Chlorine dioxide – Current regulatory processes and techniques in the EU. (Presented at the Workshop on Chlorine/Chloride Based Ballast Water Treatment, 4 March 2010, Hamburg, Germany).

LIST OF TABLES

Table 1: Chemical analysis of ballast water treated on board the

M.V. Moku Pahu , San Francisco Bay Area (Richmond, CA) Table 2: Comparison of DBP concentrations for chlorine and

chlorine dioxide treatments Table 3: Comparison of hypochlorite ion and chlorite ion

Table 4: Ecochlor ®

chlorine dioxide demand study, 4oC

Table 5: Ecochlor ®

chlorite ion demand study, 20oC Table 6: Summary of chlorine dioxide and chlorite concentrations, land-based testing Table 7: Summary of chlorine dioxide and chlorite concentrations, shipboard testing Table 8: Chlorine dioxide decay study, shipboard testing Table 9: Summary of treated ballast water substance emissions

Table 10: Re-calculated Predicted En vironmental Concentrations – MAMPEC

Table 11: Re-calculated PEC/PNEC ratios Table 12: Summary of corrosion test methods

LIST OF FIGURES

Figure 1: Chlorine species at various pH values Figure 2: Bromine species at various pH values Figure 3: Chlorine dioxide species at various pH values Figure 4: Example of chlorine dioxide demand curve, 4oC Figure 5: Example of chlorite ion demand curve, 20oC Figure 6: Chlorine dioxide decay study, shipboard testingMEPC 61/2/8 Annex, page 31

I:\MEPC\61\2-8.DOC Figure 7: Harbour definition information provided by the GESAMP-BWWG Figure 8: Emission parameter information provided by the GESAMP-BWWG Figure 9: Example of compound definition parameters

APPENDICES CONTAINED IN THE CONFIDENTIAL DOSSIER

APPENDIX 1 MAMPEC modelling documentation APPENDIX 2 Corrosion study reports APPENDIX 3 Example of Health and Safety Plan (HASP) APPENDIX 4 Chlorine dioxide analytical information

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