I:\MEPC\57\2-6.doc For reasons of economy, this document is pr inted in a limited number. Delegates are kindly asked to bring their copies to mee tings and not to request additional copies. INTERNATIONAL MARITIME ORGANIZATION

IMO 

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MARINE ENVIRONMENT PROTECTION COMMITTEE 57th session Agenda item 2 MEPC 57/2/6 7 September 2007 Original: ENGLISH



### HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Basic Approval of a ballast water management system using Active Substances

Submitted by Norway

SUMMARY

Executive summary: This document contains non-confidential information for Basic Approval of a ballast wa ter management system under the Procedure for approval of ballast water management systems that make use of Active Substances (G9) adopted by resolution MEPC.126(53). The documentation complies with the requirements related to assessments for Basic Approval.

Action to be taken: Paragraph 5

Related documents: BWM/CONF/36; MEPC 53/24/Add.1, and BWM.2/Circ.10

Introduction

1 The Ballast Water Management Convention (BWM Convention), in its regulation D-3.2, provides that ballast water managenment system s which make use of Active Substances to comply with the Convention shall be approved by the Organization.

2 The Procedure for approval of ballast water management systems that make use of Active Substances (G9) identifie s the information that should be in cluded in a proposal for approval (MEPC 53/24/Add.1, annex 4, paragraph 4.2.1) and provisions for risk characterization and analysis (MEPC 53/24/Add.1, annex 4, paragraph 5.3). Section 6 of the Procedure (G9) presents the evaluation criteria the Organization should apply in th e evaluation of the information provided in the application.

3 The competent authority in Norway has veri fied the application dossier and the test protocols applied for all tests undertaken and believe s it to satisfy the data requirements of the Procedure (G9) adopted by resolution MEPC.126(53).

4 Norway therefore submits the non-confidentia l part of the manufacturerís application dossier, in the annex of this document, to th e Organization for evaluation according to the Procedure (G9). The complete dossier will be made available to the experts of the GESAMP-Ballast Water Working Group for thei r fourth meeting with the understanding of confidential treatment.MEPC 57/2/6 - 2 -

I:\MEPC\57\2-6.doc Action requested of the Committee

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

***MEPC 57/2/6

I:\MEPC\57\2-6.doc ANNEX

NONñCONFIDENTIAL PART OF MANUFACTURERíS APPLICATION DOSSIER

The applicant proposes a ballast water management system (BWMS), comprised of a number of different processes which include the use of Acti ve Substances for the d eactivation of organisms in shipís ballast water. This deactivation is achieved thro ugh the use of cavitation, nitrogen supersaturation and disinfecti on. The disinfective Active S ubstances are produced by an electrodialytic technology someti mes referred to as electrochemi cally activation of water.

This application is based on the Procedure for approval of ballast water management systems that make use of Active Substances (G 9) and GESAMP-BWWG Draft Methodology (MEPC 56/2/2, annex 4).

Table of Contents

1 INTRODUCTION

1.1 Overview 1.2 Current status

2 THE OCEANSAVER Æ BWMS: MAIN COMPONENTS

2.1 Layout 2.2 The Mechanical Filtration Unit 2.3 The C3t Unit 2.4 The C2e Unit 2.4.1 Overall description of the unit 2.4.2 Electrochemical activation 2.5 Nitrogen Supersaturation Unit 2.6 Control & Auxiliary equipment

3 ACTIVE SUBSTANCES AND RELEVANT CHEMICALS

3.1 Definitions 3.2 Active Substances 3.3 Relevant Chemicals 3.3.1 Reaction between Active Substance and bromide ions 3.3.2 Reaction between Active Substance and nitrogen compounds 3.3.3 Reaction between Active Substa nce and organic compounds 3.4 Other chemicals

4 DATA SET FOR ACTIVE SUBSTANCES AND RELEVANT CHEMICALS

4.1 Overview of Active Substances and Relevant Chemicals 4.1.1 Active Substances 4.1.2 Relevant Chemicals 4.1.3 Other chemicals 4.1.4 Structural formulaMEPC 57/2/6 ANNEX Page 2

I:\MEPC\57\2-6.doc 4.2 Physical and chemical properties for the Acti ves Substances and Preparations and treated ballast water 4.2.1 Active Substances 4.2.2 Relevant Chemicals 4.3 Data on environmental fate and effects under aerobic and anaerobic conditions 4.3.1 Modes of degradation 4.3.2 Bioaccumulation, partition coefficient, oc tanol/water partition coefficient 4.3.3 Persistence and identification of the main metabolites in the relevant me dia (ballast water, marine and fresh waters) 4.3.4 Reaction with organic matter 4.3.5 Potential physical effects on w ildlife and benthic habitats 4.3.6 Potential residues in seafood 4.3.7 Interactive effects 4.4 Effects on aquatic plants, inverteb rates, fish and other biota 4.4.1 Hypochlorous acid 4.4.2 Hydrogen peroxide 4.4.3 Ozone 4.4.4 Chlorine dioxide 4.4.5 Bromoform 4.4.6 Dibromochloromethane 4.4.7 Dichlorobromomethane 4.4.8 2,4,6-Tribromophenol 4.4.9 Dibromoacetonitrile 4.4.10 Monobromoacetic acid 4.5 Data on mammalian toxicity 4.5.1 Hypochlorous acid 4.5.2 Hydrogen peroxide 4.5.3 Ozone 4.5.4 Chlorine dioxide 4.5.5 Bromoform 4.5.6 Dibromochloromethane 4.5.7 Dichlorobromomethane 4.5.8 2,4,6-Tribromophenol 4.5.9 Dibromoacetonitrile 4.5.10 Monobromoacetic acid

5 HANDLING AND USE OF THE OS BWMS

5.1 General 5.2 Circumferential cavitation - C3T 5.3 The C2E Unit 5.3.1 Training 5.3.2 Fire fighting measures 5.3.3 Safety issues ñ precautions 5.4 Handling and use of the nitr ogen supersaturation unit 5.4.1 General 5.4.2 Precautions to be observed at all times 5.4.3 Training 5.4.4 Handling and storage 5.4.5 Emergency measuresMEPC 57/2/6 ANNEX

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I:\MEPC\57\2-6.doc 6 RISK CHARACTERIZATION

6.1 Screening for Persistency, Bioaccumulation and Toxicity 6.1.1 The P criterion 6.1.2 The B criterion 6.1.3 The T criterion 6.2 PEC ñ PNEC assessment 6.2.1 PNEC estimation 6.2.2 PEC values in discharged ballast water 6.2.3 PEC ñ PNEC estimation 6.3 Ecotox testing of treated ballast water 6.3.1 Ecotox testing of similar systems 6.3.2 Initial ecotox testing of ballast water treate d with OS BWMS

7 RISK ASSESSMENT

7.1 Risk to safety of ship 7.1.1 Ballast water tanks 7.1.2 Ballast water pipe systems 7.2 Risk to human health 7.2.1 General 7.2.2 Precautions to be observed at all times 7.2.3 Hazards identification 7.2.4 Emergency Measures 7.2.5 Emergency First Aid 7.3 Risk to the aquatic environment

8 REFERENCESMEPC 57/2/6 ANNEX Page 4

I:\MEPC\57\2-6.doc 1 INTRODUCTION

1.1 Overview

The applicant proposes a combined ballast wate r management system (BWMS) that applies cavitation, supersaturation and di sinfection as main working prin ciples following a pre-filtration step. The system, OceanSaver Æ BWMS (OS BWMS), is the re sult of the merging of two independent research projects, following recomm endations by the Norwegian Research Council. Initially, both projects were established to de velop a complete BWMS, the common denominator being the inclusion of nitrogen supersaturation.

The OS BWMS is constructed of several componen ts which may be categorized as both ancillary components and as OceanSaver Æ components. The ancillary com ponents are industrial-type equipment developed for, and are in operation on board ships worldwide. For these components, the OS BWMS is not committed to using a sin gular manufacturer or a specific component, but rather it is more pertinent to specify equipm ent performance and deliverables. The OceanSaver Æ components, on the other hand, are specifically developed and designed for the OS BWMS and thus require a more in -depth specification.

The first component in the OS BWMS is a mechanical filtration component which pre-filters particles and organisms to the order of tens of μm (depending on filter type). The filter also includes automatic back flushing which removes the larger trapped part icles and organisms, which, at the same time contributes to the reduction of accumulated sediments in the ballast water tanks.

Apart from pre-filtration, the operational work ing principles of the OS BWMS include a dual combination of cavitation and nitr ogen supersaturation. Ballast wa ter is taken on board the ship by the use of an existing or additional ballast water pump before being s ubjected to controlled intense pressure pulses arising from hydrodynam ic cavitation. In this cas e, the cavitation is generated in a specially developed circumfe rential cavitation chamber named the C3T unit, which operates over a flow rate and pressure diffe rence range with the aid of either active or passive back pressure controls (depending on the overall configuration of the ballast water system including the ballast water tanks). Harnessed in this way, these pressure pulses are intense enough to rupture cell membranes and destroy pa rticles and organisms by forcing them to rupture, collapse or collide with one another. In order to achieve desire d flow rate capacities, identical C3T sub-units are dup licated, arranged in parallel around a circumference, and integrated in the actual ballast water pipe in a manner providing identi cal flow conditions and thus identical efficacy for each individual sub-unit.

Following exposure to cavitation, th e ballast water is then supers aturated by the injection of nitrogen before it enters the vesselís ballast water tanks. Nitr ogen supersaturation causes oxygen dissolved in the water to be re leased, leaving the water in th e tanks deficient in oxygen (hypoxic condition), thus, severely aff ecting residual organisms that are dependent on oxygen for their survival. The released oxygen and surplus nitrogen is evacuated by the use of conventional tank ventilation arrangements. In order to avoid further natural release of the nitrogen over time and to prevent potential contamination by outside air entering the ventila tion system, a pressure-vacuum device is incorporated into th e ventilation system to maintain and allow control of optimum saturation levels during a voyage.MEPC 57/2/6 ANNEX

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I:\MEPC\57\2-6.doc Additionally, in order to ensure compliant effi cacy as a function of varying ballast water properties, the system also incorporates an isolat ed (closed circuit - flow through) electrodialytic process based on the principles of an electroc hemical activation technology, the C2E process. The C2E unit applies the principle of electrochem ical activation to a small portion of the flow, (less than 0.5% by volume) producing a disinfectant which is returned to th e main flow after C3T (cavitation) exposure and nitrogen injection in order to enhance th e overall biological efficacy. The C2E unit does this by generatin g controlled amounts and variatio ns of Active Substances in situ without adding any Preparations to the water. A feature of the process is that these activated substances naturally degrade over a relative shor t period of time. Further, the efficacy of the disinfectant is enhanced by cavita tion since the cavitation causes fr agmentation and separation of bacterial colonies, etc., which expose organisms previously protected by the surrounding colony to the disinfectant, ther eby, creating a significant increase in biological effi cacy at modest dosage and concentration levels.

The OS BWMS is designed to accommodate:

.1 existing ships ñ retrofitting; .2 new ships ñ integrated design; and .3 all capacity ranges.

The development process has incorporated two prototype ship installations which are used actively as research platforms:

.1 MV Hˆegh Trooper (in operation since June 2005); and .2 MV Federal Welland (in ope ration since November 2005).

These installations are, in pr inciple, identical and have b een the subject of continuous performance assessments for a duration accumu lating to more than 40 months. These have incorporated:

- A total of 14 Biological efficacy studies (University of Bergen (UNIFOB)/ GoConsult);

- Parallel laboratory assessments of corrosion control and coating impact studies in compliance with DNVís respective standards (DNV/Safinah Ltd.);

- Installation studies including vibration an alysis (StoGda sp.zo.o Ship Design and Engineering (Poland));

- A study of the efficacy of filtration under di rty load situations. The initial filtration test was undertaken in 2005 at the research facility of NIOZ, the Netherlands (DNV/NIOZ);

- Testing of a data recording and monitoring system for functionality control of the treatment system under the EU CRAFT Pr ogramme (OceanSaver Ballast Water treatment) (Pole Star Ltd./ Houm as/MAS as/Technological Institute of Norway (TI); and

- Industrialization ñ Feasibility assessments looking at improvements with focus on sampling, system interactions includi ng shipboard automation, installation and maintenance issues, etc. For this, the vesselsí crew has been engaged in order to attain experience feedback to be used in the process of industrialization.

Additionally, development work ha s included land-based laboratory activities with the objective of improving the performance of the individu al treatment components and enhancing and exploiting potential interrelated synergies. Appr eciating the initial lack of knowledge in these respective areas, the project was fo rced to put in place its own rese arch facility. A laboratory wasMEPC 57/2/6 ANNEX Page 6

I:\MEPC\57\2-6.doc established comprising test facilities allowing tests up to 35 m 3 /hr to be undertaken (MetaFil laboratory). The test facility includes 6 simulated ballast water tanks of 1 m 3 capacity each and a feeding tank of 14 m 3 ; alternatively, the system may al so use seawater directly from the Oslo fjord. The plant is built in-house and al lows all-year opera tion. Included at the laboratory are facilities and workstations for sampling and analysis.

The resulting designs have been assessed and te sted primarily at the MetaFil laboratory at Fagerstrand (since May 2005). These assessments include:

- Principal functional assessments (e .g. confirmation studies on nitrogen consumption as a function of gas disp ersion methods and oxygen deprivation, physical characteristics in the cavitati on zone, effects of hydrodynamic imbalance, activation of seawater by electrodialysi s and insight studies including power consumption and biological efficacy, etc., ambient change and associated impacts, etc., operational SHE aspects, etc.) (DNV/ MetaFil);

- Material considerations ñ including erosion studies (MetaFil);

- Pre-assessment of the imp act of hydrodynamic cavitation of the chemical and biological properties of ballast water (University of Oldenburg ñ Germany, Institute for Chemistry and Biology in the Marine Environment, and Norwegian Institute of Water Research ñ NIVA);

- Simplified and G8 compliant biological e fficacy studies at scaled down flow rates:

30 ñ 35 m 3 / hr (DNV, NIVA)

- Toxicity tests (G9 compliant) incorporating all treatment stages (University of Oldenburg ñ Germany, NIVA).

1.2 Current Status

The OS BWMS test unit of 200 m 3 /hr capacity (operati onal range: 190 ñ 250 m 3 /hrs) was recently commissioned and G8 compliant testi ng started in June 2007 at NIVAís facility. In parallel, the system, installed on board the car carrier Hˆegh Trooper, has been upgraded to include the vessels total ballasting capacity and also including the updated C3T and C2E systems. The installed system has a capacity of 2 x 600 m 3 /hr. It is expected to be commissioned in August 2007 and will be the subject of shipboard testing in accordance with Guidelines (G8), immediately after commissioning.MEPC 57/2/6 ANNEX

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I:\MEPC\57\2-6.doc 2 THE OCEANSAVER Æ BWMS: MAIN COMPONENTS

2.1 Layout

The heart of the OS BWMS comprises four main sub-systems which are complemented by an additional part described as the control and auxili ary equipment. The four main sub-systems are:

.1 Mechanical Filtration Unit; .2 C3T Unit ñ Hydrodynamic cavitation unit; .3 C2E Unit ñ Activated water unit; and .4 Nitrogen (N 2 ) Supersaturation unit.

The system may be run in different configuratio ns depending on the level of treatment required and the particular properties of the ballast water. For example:

- Filter / C3T / C2E / N 2 Supersaturation (or in any alternative sequence); - Filter / C2E / N 2 Supersaturation (or in a ny alternative sequence); - Filter / C3T / N 2 Supersaturation (or in any alternative sequence); and - C3T/C2E (or C2E/ C3T).

In this way, the OS BWMS can be viewed as flexible and modular, and can be applied in different configurations for different end user requirements.

A principal layout of the OS BWMS is detailed in Figure 1 and is described further in the following sections. Note that the figure does not present all alternative configurations and sequence alternatives as discussed above.

Figure 1: The OS BWMS: Main Components. Water flow at uptake of Ballast Water. Filter, C2E unit and nitrogen supersatur ation are not used at discharge.MEPC 57/2/6 ANNEX Page 8

I:\MEPC\57\2-6.doc 2.2 The mechanical filtration unit

The primary task of the mechanical filtration unit in the OS BWMS is to prevent larger particles and/or organisms from entering the system. This is done, firstly, to protect the treatment plant, in particular the C3T unit, and, secondly, to enhan ce the performance of the remaining treatment stages. The mechanical filtration component re moves a considerable portion of particles and organisms of different size categories depending on the installed mesh size and type. The filter used includes an automatic back flushing pro cess which removes trappe d residue (particles, organisms). Filtration will also reduce the accu mulation of sedimentation in ballast tanks. Discharge following backflushing ta kes place only when the filter is in use at the location of ballast water uptake. The mechanical filtration un it is developed from existing industrial products made from standard marine materials. The mesh standard should be 50 μm or less of either wedgewire or weavewire type.

No Active Substances are pr oduced by the filtration unit.

2.3 The C3T unit

The (patent pending) C3T unit in the OS BWMS is a specially designed circumferential hydrodynamic cavitation chamber which is able to ge nerate, harness and control intense pressure pulses arising from cavitation. In this way, these pressure pulses are intense enough to rupture cell membranes and destroy particles and organi sms by forcing them to rupture, collapse or collide with one another. Th e use of the cavitation unit produces a mechanical effect on any micro-organisms and other living and non-living matter in the water and thus breaks down these unwanted elements and, in particular, is able to break down and weaken groups or clumps of micro-organisms into smaller-sized colonies (fragmentation). Experience gained through land-based experimental testing ha s shown that this then allows other treatment components in the system to act more efficiently.

The cavitation unit generates cavitation in the wate r by guiding the water fl ow into a carefully dimensioned circumferential constriction whereby cavitation bubbles are formed. This multiphase flow is then directed to a hi gher pressure outlet wh ere the cavitation bubbles implode. Formation and implosion of the cavit ation bubbles generates fo rces and shockwaves which affect matter in the water. The design of the geometry is such th at these effects occur across the whole of the cross-sect ion of the flow whilst being carefully balanced against pressure usage and energy loss. Using co mputational fluid dynamics (CFD) and experimental testing, a particular set of dimensions has been found to provide effective cavitat ion, particularly when treating ballast water in orde r to break down micro-organism s having a size of larger than 10 μ m. It may be noted that this is the ta rget size-range for the device operating under shipboard limitations (maximum acceptable pre ssure loss). Cavitation will also affect organism-categories outside th e range as described above.

Literature studies carried out by OceanSaver (B ehrends 2006, NIVA 2006) indicated that Active Substances from a theoretical point of view c ould be produced during ballast water treatment by hydrodynamic cavitation as a result of formation of free radicals in natural seawater. However, no alteration of the chemical and biological pr operties of the tested seawater was found in a follow-up study (Behrends et al , 2007) and the cavitated water di d not show any toxic properties directly after treatment and after eight days on two different marine organisms, the bacterium Vibrio fischeri and the brine shrimp Artemia salina

.MEPC 57/2/6 ANNEX

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I:\MEPC\57\2-6.doc Our conclusion is, therefore, that no Active Substa nces are produced in dete ctable levels by the C3T unit.

Figure 2 illustrates the perfor mance characteristics of the standard C3T sub-unit.

Figure 2: C3T cavitation characteristics

2.4 The C2E unit

2.4.1 Overall description of the unit

The C2E unit (patent pending) incorporated in the OS BWMS consists of three main components: the automation and control system; th e DC converter/ rectifier power supply; and an electrodialytic activation cell module ñ in which a flow is separated by means of a membrane/diaphragm which allows exposure of the ballast water to a positive or a negative charge only at a constant current level. The C2 E unit produces electrochemically activated water, which when applied in combination with filtr ation, supersaturation a nd cavitation, enhances overall biological efficacy in pa rticular for the smaller groups of organisms defined in the D-2 standard of the Ballast Water Mana gement Convention. The C2E unit does this by generating controlled amounts and va riations of Active Substances in situ and only in a side stream of the main ballast wa ter stream without adding any a dditional chemicals (Preparations) to the water. Frequenc y distribution of the implodin g cavitation bubbles produced by an individual C3T sub-unit. The unit g enerates more than 100,000 pressure pulses per second.

Pressure pulse characteristicsproduced by an individual C3T subunit. The unit g enerates acoustic pressure peaks exceeding 10,000 Pa.MEPC 57/2/6 ANNEX Page 10

I:\MEPC\57\2-6.doc A side stream of the ballast water is treated in the electrodialytic activation cell and then re-injected into the ballast wate r line. Typically, le ss than 0.5% by volume of the total water flow into the OS BWMS passes through the C2 E unit (electrodialytic activation cell(s)). The product of the electrodialytic activation ce ll has the effect of disabling or killing micro-organisms, and can also have a benefici al effect on treating organic compounds in the

water.

Studies carried out during the development of the OS BWMS have demonstrated that by directing only a part of the water through the electrodialytic activation cell and returning a product of the electrodialytic activa tion cell to the water, an effec tive water treatment is achieved without the need to treat the entire water flow . This reduces the amount of electrical power required to carry out the water tr eatment. In addition, the system can be made smaller compared to existing water treatment systems due to the co mparatively smaller volume of water treated by the electrochemical activation cell in order to ob tain an overall treatmen t effect on the whole volume of ballast water.

The portion of the ballast water treated by the elect rodialytic activation cell is separated from the incoming water flow following filtration and pr ior to cavitation and then passes through the electrodialytic activatio n cell as the remainder of the wate r passes by, without being treated by the electrodialytic activa tion cell (illustrated in the schematic presentation in Figure 1). Thus, the C2E unit includes a main flow path, whereby the inle t flow path is arranged to separate a portion of the flow from the main flow path and direct it through the electrodialytic activation cell. Alternatively, the part of the water treated by th e electrodialytic activati on cell can be provided from a separate source, for example an external source of brine or saltwat er (or brine/saltwater mixed with the bypass from the incoming flow (bal last water)). In both cases, the apparatus may include a connection from the outlet of the C2E un it to a main flow path, whereby the product of the electrochemical activation cell is added to the main flow path.

The C2E process is close-circuited and does not require any holding tanks or dosage pumps as it utilizes the pressure loss over the C3T unit to drive the take-off and re-injection. There are no residual flow or discharge/waste requirements asso ciated to the process. The components used in the C2E unit are standard indus trial products for shipboard us e with the exception of the electrodialytic cell which is unique to the OS BW MS. The capacity of the C2E unit is matched in a similar way as to that of the C3T unit by applying the concept of modular duplication.

2.4.2 Electrochemical activation

The principle of electrochemical activation is applied to treat water in a variety of applications including wastewater (e.g. Folsom et al . 1994, Anon. 2 006, Prilutsky et al . 2003, Yang et al . 1999, Swem et al . 2001, Stroud et al . 2001), swimming pools and potabl e water. The principal process of the C2E unit is that of applying an electric potential difference between two electrodes to the water flow separated by a membrane/diaphragm ( electrodialytic process) . The ion selective membrane separates the anolyte and the catholyte flows and allo ws the concentration of ions which result in the formation of meta stable ions and free radicals. In conventional electrolysis of seawater, most of the complex r eactive species formed at the anode and cathode react with each other and are largely neutralized immediatel y, requiring a high level of charge to create biological effects. In conven tional electrolysis, hypochlorous acid is the dominant stable constituent formed.MEPC 57/2/6 ANNEX Page 11

I:\MEPC\57\2-6.doc In the C2E process, however, the anolyte solu tion has higher microbial efficacy than normal electrolysis (chlorine based) so lutions when compared in terms of measurable active chlorine present in solution. As a result, the anolyte has superior steri lizing and disinfect ant properties, since the reactive species present in the so lution are more effective in destroying micro-organisms and organic mol ecules than chlorine alone.

The catholyte effluent is alkalin e (pH ~ 10-12) and the anolyte effluent is acidic (pH ~ 2.4-4). The pH in the anolyte may be adjusted by mixing some or all of the catholyt e into the effluent. In the C2E unit, approximately 50% of the catholyte is mixed with the anolyte resulting in a pH around 3 before the side stream is injected into th e ballast line. Catholyte is recirculated in the cell avoiding waste issues.

The C2E cell module configuration and application, as described in this document, is patent pending. The capacity of the C2E unit is matched si milarly to that of the C3T unit by applying the concept of modular duplication (including the powering system).

Item Description 1 Cathode (-ve Electrode) 2 Anode (+ve Electrode) 3 Membrane 4 Body 5 Anolyte Production Zone 6 Catholyte Production Zone 7 Seawater Inlet 8 Anolyte/Catholyte Mixture Outlet 9 Catholyte Take-Off Valve 10 Catholyte Outlet

Figure 3: Operational principle of the C2E

The ratio between the overall amount of water and the amount of water flowing into and out of the electrochemical activation cell is near constant (following any pressure variations in the main ballast line), thus, the dosage of the C2E di sinfectant by volume is c onstant. Any necessary alterations regarding the concentration of Active Substances in the disi nfectant produced over the cells are achieved by changing the le vel of applied electrical current (amperage) and adjusting the injection of catholyte. Changes to the necessary settings are indicated by comparing the Oxygen Reduction Potential (ORP), Free Available Chlori ne levels and pH measured in a calibrationMEPC 57/2/6 ANNEX Page 12

I:\MEPC\57\2-6.doc loop to measurements taken from a monitoring point downstream of the injection point (main ballast line). This is th en used as a basis for the adju stments during operation. The ranges for desired values of ORP and FAC may be, respectively, 350 ñ 800 mV and 0.05 ñ 2 ppm, more preferably, 350 ñ 550 mV and 0.5 ñ 1.5 ppm. When the ORP and/or FAC measured values are outside these ranges, then the operation of the electrochemical activation cell is adjusted accordingly.

As the ballast water is stored for a period of time after treatment, this allows for the oxidants and reactive Substances from the product of the electr ochemical activation cell to have full effect on any micro-organisms and other unwanted matter in th e water. In the case of ballast water, there is generally a reasonable time of storage as the ship moves from port to port before re-loading with cargo and discharging the ba llast water. This time can be advantageously put to use by allowing the product of the electrochemical activati on cell to take effect. Experience has verified the short duration in which these characteristic values (ORP/ FAC) are elevated. FAC levels are typically halved within 6 ñ 8 hours.

Active Substances and Related Substances will be described in more detail from section 3 and following sections.

2.5 Nitrogen Supersaturation Unit

In the OS BWMS, a gas injection/mixing unit is provided for the injection of nitrogen (N 2 ) gas into the ballast water. Nitrogen may be injected in to all or a part of the water flow (typically less than 15% of the total water flow) with the main criteria being that the nitrogen is injected in sufficient amounts to ensure that the treated water when reaching the ballast tanks is supersaturated with nitrogen to a level of around 120-135% supersaturation providing a reduced level of dissolved oxygen of 2.5 mg/litre or le ss. The OS BWMS applies conventional static mixers to all gas mixing points. In general, a two-stage dispersion process has proven more efficient with respect to gas consumption. Thus, current the configurations apply a two-stage gas dispersion principle.

In the OS BWMS, N 2 requirements are met either by on- board production using standard N 2 membrane generators that work by filtering normal ai r or by shore supply in storage tanks. For most vessels, the latter means of su pply is considered less practical. N 2 is an inert gas, thus N 2 generators are currently found in use on bo ard ships for purposes including controlled atmospheres (in reefers), for safety-blanketing on board chemical carriers/LPG-carriers and for gas-leakage control on board LNG-carriers. Thus, both the N 2 generator as well as the compressor are often critical components for the safety of the vessel and are highly evolved for shipboard use. It may be noted that an N 2 generating unit comprises a compressor and a membrane-based unit, allowing nitrogen to be separated from air by resting on the principle that different gases will pass through membranes at significantly different rates, thus permitting separation.

The OS BWMS comprises either a storage of pressurized N 2 or one or more N 2 generating units. Operational experience applying such units for s upersaturating ballast water in-line on uptake has been obtained from the operation of the MV Hˆegh Trooper and MV Federal Welland

. The units are type approved for sh ipboard use or subject to a functionality test to be witnessed by class.MEPC 57/2/6 ANNEX Page 13

I:\MEPC\57\2-6.doc Ballast water is supersaturated by the injection of N 2 before it enters the vesselís ballast water tanks. Nitrogen supersaturation causes dissolved oxygen to be released, l eaving the water in the tanks deficient in oxygen (a hypoxic condition) , thus, offering as a means of preventing re-growth and severely affecting organisms that are dependent on oxygen for their survival. The supersaturation of nitrogen also reduces corr osion and the weathering of corrosion protection systems such as coatings and paints as oxidation is a cause of such co rrosion and weathering. This is particularly useful when water is ta ken into a ballast tank, as otherwise, the oxygen naturally present in the ballast wate r can lead to this failure mode.

In order to achieve the requi red level of supers aturation/oxygen depriv ation, the capacity requirement for nitrogen injection at this purity has been specified at maximum 0.2 kg/m 3

. This relationship is linear a nd can be scaled up accordingly.

Nitrogen supersaturation and cons equently oxygen deprivation will impact the living conditions of organisms present in the treated water. Ho wever, the process does not cause any chemical reactions or lead to the formation of new chemi cal compounds. At discharge, the treated water is aired to avoid discharge of hypoxic water. It is therefore our conclusion that no Active Substances are produced by the application of nitr ogen supersaturation when applied as discussed in this document.

2.6 Control and auxiliary equipment

Several additional elements in the OS BWMS act as control and auxiliary equipment. These components can be regarded as standard ìoff-the-shelfî components commonly used in the marine industry and as such, do not require much explanation. A summary of the purpose of these components is, however, provided as follows:

Booster Pump

The booster pump caters for the additional pressure requirements of the specific system under consideration. The additi onal pressure requirements s upply the driving energy for the cavitation process and compensate for additional pressure losses incurred by the system that arise through the addition of th e mechanical filter, piping system etc. For example, the C3T unit has been found to operate within IMO guidelines with an upstream pressure immediately in front of th e unit between 4 ñ 5 barg. The unit induces a pressure loss of approximately 2 ñ 2.5 barg.

In the case of a retrof it, the booster pump may be an additional standard component that is installed in addition to the existing shipís ballast water pump. Th e sizing of the booster pump depends upon the particular system unde r consideration. Alte rnatively, one may choose to upgrade the delivery pressure from the existing ballast water pump(s) if possible, or alternatively ch ange the ballast pump to a pump that meets the overall specifications of the OS BWMS. The booste r pump is constructed from standard materials commonly used in ballast water pum ps today and requires similar installation and routine maintenance.

In a new ship, the additional pressure requi rements would be take n into account when initial sizing and pressure requirements of the new system are carried out.MEPC 57/2/6 ANNEX Page 14

I:\MEPC\57\2-6.doc Minimum Pressure Control

The OceanSaver Æ research programme has identified optimum operational parameters for the C3T unit including the optim ization of implosion pressu res, frequency of collapse and, consequently, biological efficacy in li ght of overall considerations including shipboard interface issues. The overall efficiency of the unit is great ly improved when the back pressure is maintained above a minimum level. However, during filling or empting of the ballast water tanks, the system back pressure against which the C3T unit works will vary. Therefore, a standard industrial pre ssure management device may be applied to maintain the pressure to the C3T unit within acceptable levels. This device may be passive or active (e.g. a constant pressure valve). Note that sy stem backpressure will vary according to tank and piping configurations of the specific ship (e.g. pressure build-up characteristics of the vessels ballast water tanks during filling) and need to be addressed specifically (standard pressure calculations) when specifying the overall ballast water system requirements (pipe size, pump capacity, etc.).

Pressure/Vacuum Valve

The Pressure/Vacuum valve (PVV) is a device designed to maintain pressure and vacuum conditions in the individual ballast tank so th at pressure exposure does not exceed that of its design criteria. Such devices are available ìoff the shelfî for ìdryî operations. In the OS BWMS, such valves are applie d in order to maintain the N 2 blanket over the treated ballast water in order to maintain the required level of N 2 supersaturation and the achieved deficiency of oxygen in the water in the tank. In addition to providing protection against under pressurizing/overpressurizing of the ballast tank, they also prevent air intake and evaporative losses Thes e pressure vacuum valves maintain a tight seal until the tanks overpressure or underp ressure exceeds the set minimum or maximum pressure threshold values to which the valv es are designed. Then the valves allow for intake of air or discharge of N 2 , air or water, until the pressu re in the tank is within the acceptable range.

PVV are used in industry in different areas for the purpose of securing pressure safe ventilation. The OS BWMS application introdu ces the presence of wa ter as well as gas and, consequently, it has been necessary to develop a valve that manages both. The OS PVV has recently undergone considerations by class for certification and is now the only type approved PVV available for ìwet atmospheresî in the market.

Power and Continuous Monitoring

In addition to the components above, there is al so an integrated power control system that ensures the correct power supply to a ll components and items at all times.

Various control sensors and monitoring equipmen t are installed to measure variables such as pump speed and frequency, power, current, voltage, flowrate, pressure, temperature, hydrophone data, dissolved oxygen levels, ORP and free residual oxidant. Data from these are recorded and used for system cont rol in an integrated system automation loop. Appropriate safety features including alar ms/warning systems and shut-down procedures are also included. The perfor mance of the system may be continuously monitored by use of automatic monitoring and data transfer via satellite services such as PurpleFinder. This feature has been extensively assessed over the last two years as it has been applied to both the vessels included in the research programme.MEPC 57/2/6 ANNEX Page 15

I:\MEPC\57\2-6.doc 3 ACTIVE SUBSTANCES AND RELEVANT CHEMICALS

3.1 Definitions

The component of the OS BWMS deemed relevant for Active Substances approval by this application is the C2E unit. In th is application, we will use the de finitions of ìActive Substanceî, ìRelevant Chemicalsî from Procedure for approval of ballast water management systems that make use of Active Substances (G9).

Active Substances are produced in the anode chambe r and to some extent in the cathode chamber of the C2E unit. However, several of these s ubstances are very short-lived, but may produce other chemicals that have effects relevant for Human Exposure Scenario (HES) aspects. These reaction products are here defined as Rele vant Chemicals together with other possible by-products that may be produced by the treatment in the ballast tanks or after discharge.

The purpose of the nitrogen supers aturation unit is mainly to redu ce corrosion in the ballast tanks by replacing oxygen by the in ert gas nitrogen. Consequently, this is not an Ac tive Substance. However, nitrogen supersaturation may have eff ects on some organisms and may be of concern for the safety of the crew. The applicant has de fined it as ìOther compon entsî and included some relevant information for this as well.

In the following sections, Active Substances and Relevant Chemicals are defined more precisely. The following sections will describe the particular chemicals, environmental and safety features, discharge characteristics and resulting characterist ics of the treated ballas t water as required by the Draft Methodology of the GESAMP-BWWG.

3.2 Active Substances

The electrolytic process in the C2E unit produces an anolyte and a catholyte in separate chambers, separated by a diaphragm. The anolyte, which is acidic, is a mixture of short-lived oxidative agents, with a documented toxic effect to living organisms. The catholyte, which is alkaline, poses a reductive, bu t limited toxic effect to the organisms. In the C2E unit, approximately 50% of the catholyte is circulated into the anode ch amber resulting in a pH in the Active Substance mixture of around 3 before it is injected into the main ballast line.

Most literature discussing the pr oducts of electrolysis of water is concerned with brine solutions (Brine is water saturated or nearly saturated with sodi um chloride (NaCl)).

Due to its chemical features (T extbox 1) the electrolysis of seawater results in several other compounds compared to brine. Alkaline conditions at the cathode electrolysis of seawater result in a mineral deposition which precipitates calcium and magnesium minerals from seawater:

OH - + HCO 3- + Ca 2+ = CaCO 3 + H 2 O 2OH - + Mg 2+ = Mg(OH) 2 Textbox 1: Main components of seawater (35 psu) (Wilson 1975): Element mg/L Cl - 19 354 Na + 10 770 Mg 2+ 1 290 SO 4 2- 2 712 Ca 2+ 412 K + 399 Br - 67 HCO 3- , CO 3 2- , CO 2 28 Sr 2+ 7.9 B 4.5 F - 1.3MEPC 57/2/6 ANNEX Page 16

I:\MEPC\57\2-6.doc Below is listed some of the reactions that form Active Substances found in the literature when electrolysing seawater. Due to the large number of possible reactions it is not intended to present a complete list, but some of the most re levant for this application are included.



## ( ) ( ) ( )

( ) ( ) ( )

( ) ( ) ( ) ( ) 10 3 2 9 6 6 3 8 5 2 4 7 6 2 2 5 4 3 2 2 2 1 2 2 :

2 3 2 3

2 2 2 2 2 2 2 2

2 2 2 2 2 2 2

− − − −

− − − − + − − − − − − −

−

+ + → + + + → + + → + + + → + + → → • + • + • → + + → + + → + +

→

e O H O OH O e O O H e O H ClO OH Cl O H O HCl O H HClO e O H OH O H OH H OH e OH OH e O H ClO OH Cl HCl HClO O H Cl e Cl Cl reactions Anode

Reaction (1) is the principal anode reaction (Wh ite 1999). However, most of the chlorine gas reacts rapidly with water and produce hypochlorous acid (2) as the dominant oxidant in the anolyte. In seawater, the three species of chlorine (Cl 2 , HOCl, and OCl - ) are in equilibrium as a function of pH, temperature, salin ity and other factors. An example of the distribution between the two most abundant in coastal water is pres ented in Figure 4. At a salinity of 32 psu, temperature 15oC and pH 8.2, 89% of the chlorine is present as OCl - and only 11% as hypochlorous acid. The pH in the anolyte from th e C2E unit is around 3, which means that nearly all chlorine is hypochlorous acid and some as chlorine gas. ) 11 ( 2 2 2 :

2 2 − − +

→ + OH H e O H reactions CathodeMEPC 57/2/6 ANNEX Page 17

I:\MEPC\57\2-6.doc Figure 4: The calculated variation in comp osition of two most abundant components of the chlorine equilibrium in seawater (temperature 15oC, salinity 21 psu). Common pH range in seawater is marked with a square.

Reaction (11) is the principal cathode reaction. Hydrogen gas has no environmental effects, but has safety concerns. When hydrogen gas is formed , the catholyte become highly alkaline due to high concentrations of OH - . The porous membrane separating the anode and cathode chamber is used to inhibit the migration of the OH - ions from the cathode to the anode; otherwise, the mixing of these solutions would result in the formation of hypochlor ite as the dominant oxidant.

NIVA (2007a) estimated the active compounds fo rmed in the anolyte from the C2E unit quantitatively using more or less specific methods of determination.

Table 1: Active Substances produced by the C2E unit using seawater. Compounds are quantified within 2-10 min (NIVA 2007a)

Test water Total chlorine mg Cl 2 /L Free chlorine mg Cl 2 /L Combined chlorine mg Cl 2 /L Ozone mg O 3 /L Hydrogen peroxide mg H 2 O 2 /L High salinity 34 psu 1010 980 30 13.7 2.7 Brackish water 17 psu 870 800 70 5.4 2.1 Surface water 20 psu 970 930 40 10.9 3.6

An analysis by Tallinn Technical University (Trapido et al . 1999) of anolyte produced from brine in a comparable dialytic cell to the C2E conclude d that the anolyte contained the following active forms of chlorine: hypochlorous acid (HClO), hypoc hlorous ion (ClO - ) and chlorine gas (Cl 2 ). No presence of chlorite (ClO 2 − ) or chlorate (ClO 3 − ) ions was found in the anolyte using ion chromatography.

Based on available information, the applicant conc luded that the Active Substances formed in the C2E unit is primarily hypochlorous acid (HClO) with concentrations of chlorine gas (Cl 2 ), Ozone (O 3 ), hydrogen peroxide (H 2 O 2 ), chlorine dioxide (ClO 2 ) and hypochlorite (ClO - ). 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

pHFraction HOCl OCl-MEPC 57/2/6 ANNEX Page 18

I:\MEPC\57\2-6.doc In relevant databases and literature, there are almost no data on hypochlorous acid (HClO) and hypochlorite ion (ClO - ) necessary for the evaluation in th e Procedure for approval of ballast water management systems that make use of of Active Substances (G9). This is because the mixture is not available as a preparation on the market. To compensate, the applicant mainly uses data relating to sodium hypoc hlorite (NaClO) as reference data for the evaluation of the free active chlorine in this application. NaClO rapidl y hydrolyses in water and resides there as free active chlorine. Thus, the HClO and ClO - could be evaluated us ing data on NaClO.

3.3 Relevant Chemicals

Apart from the primary anodic and cathodic reac tions, there are second ary reactions producing Relevant Chemicals, some with documented t oxic effect. As these Relevant Chemicals are dependent to some part on the quality of the seaw ater, and the seawater temperature, it is quite difficult to give a full estimate of all possible substances that might occur. Chlorination and electrolysis of seawater is commonly used as an ti-biofouling measure in cooling water circuits in European coastal and estuarine power stations. Taylor (2006) and Jenner et al . (1998) reviewed the outcome of research on chlorination by-pr oducts (CBPs) which can be produced from electrolysis of estuarine or seawater and ge nerated through reactions between halogen oxidants and organic matter in the water. The following sec tions are based on these papers together with general textbook information on halogen oxidants and seawater chemistry.

Sugam and Helz (1981) considered 25 different Cl and Br species in chlorinated marine waters and found that, for salinities above 3 psu, the following five species would be the important contributors to the labile fraction of pr oduced oxidants at pH 6-8: HOBr, OBr - , NH 2 Br, NHBr 2 and NBr 3

.

3.3.1 Reaction between Active Substance and bromide ions

All substances produced in both the anolyte and the catholyte are relative s hort-lived oxidative or reductive substances. Owing to the presence of br omine in the seawater (Textbox 1) in excess concentrations to the chlorine a pplied in the OS BWMS, chlorine r eacts with the bromide ions to form hypobromous acid (Farkas et al. 1988) when the anolyte is injected into the ballast line:



### ) 12 (

− − 

### +

→ + Cl HOBr Br HOCl

Textbox 2: Chlorine oxidants are described in the literat ure as ìfreeî, ìactiveî, ìavailableî, ìcombinedî or ìresidualî, and by combinations of these adjectives as well (definitions from Jenner et al. 1998, Eidnes & Aareskjold 1992, NIVA 2007a) 1. Free oxidant/Free available oxidant in seawater is pres ent mainly as an equilibrium mixture of hypochlorous acid, hypochlorite ions, hypobromous acid and hypobromite ion. 2. Combined oxidant/Combined available oxidant is available as bromamines, chloramines or other compounds having an N-C link. These are also ox idants but less effective than the free oxidants. 3. Total available oxidant/Total free oxidant is the sum of (1) and (2). 4. Total residual oxidant (TRO) is i dentical to (3), but emphasise the conc ept of pool of oxy-disinfectant capacity that persists after the init ial demand (see below) has been met. 5. Oxidant initial demand is defined as the difference between the amount of oxidant added and the useful (residual) oxidant (TRO) remaining at t he end of a specifie d contact period. 6. Oxidant decay is a continuing serie of reactions t hat will in time lead to a complete disappearance of all measurable oxidant.MEPC 57/2/6 ANNEX Page 19

I:\MEPC\57\2-6.doc The reaction rate between chlorine and bromide ion is rapid. W ith assumed seawater conditions (35 psu, 25oC, pH 8.3), Selleck et al . (1976) calculated the time required to convert 99% of the chlorine to bromine to be around 10 seconds.

Similar to hypoclorous acid, hypobromous acid (HOBr) will dissociate depending upon pH, temperature and salinity. However, at pH 8 and normal salinities and temperatures for seawater, the un b dissociated HOBr can be calculated to approximately 83% versus HOCl at only 28%. Consequently, the presence of bromine increases the biological efficacy of the OS BWMS.

3.3.2 Reaction between Active Substance and nitrogen compounds

Inorganic nitrogen (ammonia, nitrite and nitrat e) and organic nitrogen (amino acids, proteins) reside in natural seawater as nitrogen compounds. Some of th e hypochlorous acid and hypobromous acid react with these nitrogen compounds and form N-chloro or N-bromo compounds, commonly called halogenamines. There are two distinct classes ñ organic and inorganic.

If water contains ammonia nitrogen, inorganic chloro- and bromamines will be formed rapidly (e.g. NH 2 Br, NHBr 2 and NHBr 3 ). Changing the pH value, infl uences the amount of mono-, diand tribromamine that is formed. According to reaction rates establis hed by Morris (1952, 1965) (cited in White 1999), the fast est conversion of HOCl to NH 2 Cl occurs at pH 8.3 which is the normal pH of seawater. The reaction slows appreci able as temperature drops. Dichloramine and trichloramine will form at pH around 8 if excess chlorine is available (White 1999).

All halogenamines are included in the measured to tal available oxidant or total residual oxidant (TRO) (Textbox 2).

3.3.3 Reaction between Active Substance and organic compounds

Other Relevant Chemicals are so-called Disinfec tion By-Products (DBPs) that are both organic and inorganic substances formed when Active Substances react with naturally occurring compounds in the water. DBPs are normally formed in reactions where organic chemicals play a major part.

A relatively limited number of studies appear to have focused on DBP formation in marine waters. Most of the studies have analysed chlo rinated cooling water samples from coastal and estuarine power stations. Some of the most rele vant studies have been summarized in Table 2 together with results from direct measurements on samples collected during an initial full-scale testing of the OS BWMS.MEPC 57/2/6 ANNEX Page 20

I:\MEPC\57\2-6.doc Table 2: Summary of results from relevant studies on chlorination of marine waters. Results from direct measurements on sample s collected during a preliminaryfull-scale testing of the OS BWMS at Solbergstrand summer 2007 are also shown (- = not analysed).

OceanSaver© Taylor (2006) Allonier et al

. (1999) Fabbricino & Korshin (2005)

Contr. Test day 0 Test day 5 Before After 0.2-0.8

mg Cl 2 /l 5 mg Cl 2 /l Coastal

water 1 mg Cl 2 /l Deep
water 1 mg Cl 2 /l Chemical Name μg/l μg/l μg /l μg/l μg/l μg/l μg/l μg/l μg/l AOX 29 386 1290 EOX <50 <50 <50 0.3-2.4 1-13 2- monochlorophenol <0.1 <0.1 <0.1

3- monochlorophenol <0.1 <0.1 <0.1

4- monochlorophenol <0.1 <0.1 <0.1

2,3-dichlorophenol <0.1 <0.1 <0.1 2,4+2,5- dichlorophenol <0.2 <0.2 <0.2 <0.4 <0.4

2,6-dichlorophenol <0.1 <0.1 <0.1 3,4-dichlorophenol <0.1 <0.1 <0.1 3,5-dichlorophenol <0.1 <0.1 <0.1 2,3,4- trichlorophenol <0.1 <0.1 <0.1

2,3,5- trichlorophenol <0.1 <0.1 <0.1

2,3,6- trichlorophenol <0.1 <0.1 <0.1

2,4,5- trichlorophenol <0.1 <0.1 <0.1

2,4,6- trichlorophenol <0.1 <0.1 <0.1 <0.06 <0.0 6 3,4,5- trichlorophenol <0.1 <0.1 <0.1

2,3,4,5- tetrachlorophenol <0.1 <0.1 <0.1

2,3,4,6- tetrachlorophenol <0.1 <0.1 <0.1

2,3,5,6- tetrachlorophenol <0.1 <0.1 <0.1

pentachlorophenol <0.1 <0.1 <0.1 trichloromethane/ chloroform <0.3 <0.3 <0.3 <0.1 <0.1- 0.3 <2 ca 0.2 ca 0.2

tribromomethane/ bromoform <0.1 385 398 <0.1- 1.0 1-43 7-27 130- 170 ca 105 ca 10MEPC 57/2/6 ANNEX Page 21

I:\MEPC\57\2-6.docDibromochloromethane <0.1 14.7 17.8 <0.1 0.1- 2.2 5-10 ca 3 ca 0.3

Dichlorobromomethane <0.1 0.297 0.337 <0.1 0.1- 1.0 <1 ca 0.2 < 0.1

Monochloroacetic acid - - - <1 <1 <1 ca 1

Dichloroacetic acid - - - <1 <1 <1 ca 1 Trichloroacteic acid - - - <1 <1 <1 ca 7

Monobromoacetic acid - - - <1 <1-5 2-3 ca 2 <1

Dibromoacetic acid - - - <2 <2- 10 7.3- 10.2 11- 28 ca 16 ca 3

Tribromoacetic acid - - - ca 75 n/a

Bromochloroacetic acid - - - <1 n/a

Dibromochloroacet ic acid - - - 3-4 ca 1 n/a

Bromodichloroacet ic acid - - - <1 ca 3

Monobromoacetonitrile - - - 0-5

Dibromoacetonitril

e - - - <0.1 0.1- 5.0 0.9-3.6 ca 23 ca 3.8 n/a

Bromochloroacetonitrile - - - ca 0.1 ca 0.02

2,4-dibromophenol - - - <0.02 <0.0 2 2,6-dibromophenol - - - <0.1 <0.1 2,4,6- tribromophenol - - - <0.05 <0.0 5-0.3 0.1- 0.37 1.6

Dibromoethane - - - 0.1 0.7 1,2,3- trichloropropane - - - 0.2 15.8

2-chlorotoluene - - - 0.1 2.2 4-chlorotoluene - - - 0.1 1.3 1,2-dibromo-3- chloropropane - - - <0.1 1.2

1,2,3- tribromobenzene - - - <0.1 1.1

In this initial test of the OS BWMS, the chlori ne concentrations used were higher (3-4 mg/L) than normal operation (1.5 ñ 2.5 mg/L). Further analyses of samples taken during the full-scale test, with normal concentrations of chlori ne, will include chemicals found by Taylor (2006) (see Table 2).

From the literature review and preliminary analyses, the main Relevant Chemicals have been selected and shown in Table 3.MEPC 57/2/6 ANNEX Page 22

I:\MEPC\57\2-6.doc Table 3: Main Relevant Chemicals expected to be produced using the C2E unit

Chemical Name Empirical formula

trichloromethane/chloroform CHCl 3 tribromomethane/bromoform CHBr 3 Dibromochloromethane CHBr 2 Cl Dichlorobromomethane CHBrCl 2 Trichloroacetic acid C 2 HCl 3 O 2 Monobromoacetic acid C 2 H 3 BrO 2 Dibromoacetic acid C 2 H 2 Br 2 O 2 Tribromoacetic acid C 2 HBr 3 O 2 Dibromochloroacetic acid C 2 HBr 2 ClO 2 Bromodichloroacetic acid C 2 HBrCl 2 O 2 Monobromoacetonitrile C 2 H 2 BrN Dibromoacetonitrile C 2 HBr 2 N 2,4,6-tribromophenol C 6 H 3 Br 3 O Dibromoethane C 2 H 4 Br 2 1,2,3-trichloropropane C 3 H 5 Cl 3 2-chlorotoluene C 7 H 7 Cl 4-chlorotoluene C 7 H 7 Cl 1,2-dibromo-3-chloropropane C 3 H 5 Br 2 Cl 1,2,3-tribromobenzene C 6 H 3 Br 3

3.4 Other chemicals

Nitrogen (N 2 ) is the most abundant gas in the atmosphere and in the ocean (T able 4). It is not used directly by living organisms except for cert ain bacteria and concentrations in the water column are, therefore, driven by physical processes.

Table 4: The percentage by volume of gases in the atmosphere and in seawater

Gas Percentage by volume in atmosphere Percentage by volume in surface

seawater 1 Nitrogen (N 2 ) 78.03 48 Oxygen (O 2 ) 20.99 36 Carbon dioxide (CO 2 ) 0.03 15 Argon, Helium, Neon, etc. (Ar, He, Ne) 0.95 1

totals 100 100

1 Salinity = 36 psu, Temperature 20oC

The solubility of gases in water varies with te mperature and salinity. In natural seawater, the supersaturation of inert gases, such as nitr ogen, is primarily cont rolled by diffusive and bubble-mediated air-sea gas exch ange as well as by temperat ure change and atmospheric pressure. Observations from coastal waters show that bubbles can be transported to a depth of two to three times the prevailing wave height, th us enhancing gas transfer into the water by wayMEPC 57/2/6 ANNEX Page 23

I:\MEPC\57\2-6.doc of hydrostatic pressure (Atkinson 1973). Supers aturation of natural seawater with oxygen at 130% and nitrogen at 120% of air saturation are measured.

There are several reports of fish mortality fr om natural water supersaturated with nitrogen including sea trout, la rge scale menhaden ( Brevoortia patronus ), bay anchovies ( Anchoa mitchilli ), Atlantic croakers ( Micropogon undulatus ), eels ( Myrophis punctatus ), and longnose gar ( Lepisosteus osseus ) (Renfro 1963, Baath et al. 1989, Machado 1989). Gas bubble disease was identified as the cause of death. Increased mo rtality caused by IPN virus in rainbow trout has been observed from as low as 103% supersatur ation after long time e xposure (weeks ñ months) and gas bubble disease has been observed after 60 days exposur e at 5% supersaturation. There are, however, few, if any, observations of effects after short time exposure (hours ñ days) by less than 110% supersaturation (Jensen et al. 1986).

The biological effects of supersat uration in natural waters are much smaller than in laboratory experiments (Heggberget 1984) probably because fish and other mobile organisms may avoid supersaturated water (Stickney 1968).

Three experiments have been iden tified testing nitrogen (air) supers aturation as a possible ballast water treatment technology:

- Tamburri et al . (2001) testing deoxygenation of ballast water by nitrogen supersaturation and effects on juve niles of three species (polychaet Ficopomatus enigmaticus , zebra mussel Dreissena polymorpha , and green crab Carcinus

maenas ).

- Jelmert (2001) testing eff ects of air supersaturated water on two species (brine shrimp Artemia sp. and juveniles of the common mollusc Mytilus edulis ).

- Dragsund et al . (2002) testing biological efficacy of nitrogen supersaturation in a small scale (< 3m 3 /hr) ballast water treatment test facility.

Nitrogen gas is an inert, non-toxic and non-bioaccu mulating element. The biological effects of nitrogen supersaturation are mainly due to deoxy genation of the water. In the following text, the nitrogen supersaturation unit is therefore only di scussed in relation to safety aspects regarding ambient air quality in the engi ne room and ballast tanks.MEPC 57/2/6 ANNEX Page 24

I:\MEPC\57\2-6.doc 4 DATA SET FOR ACTIVE SUBSTANC ES AND RELEVANT CHEMICALS

4.1 Overview of Active Substances and Relevant Chemicals

4.1.1 Active Substances

Component Chemical Name CAS Number UN Number Molecular Weight (g/mol) Empirical formula Hypochlorous acid 7790-92-3 n/a 52.460 HOCl Hydrogen peroxide 7722-84-1 2015 34.015 H 2 O 2 Ozone 10028-15-6 47.998 O 3 Chlorine dioxide 10049-04-4 9191 69.5 ClO 2

4.1.2 Relevant Chemicals

Component Chemical Name CAS Number UN Number Molecular Weight (g/mol) Empirical formula Bromoform 75-25-2 2515 252.731 CHBr 3 Dibromochloromethane 124-48-1 2810 208.290 CHBr 2 Cl Dichlorobromomethane 75-27-4 8027 163.83 CHBrCl 2 2, 4, 6 - Tribromophenol 118-79-6 2811 330.82 C 6 H 3 Br 3 O

Dibromoacetonitrile 3252-43- 5 2810 198.86 C 2 HBr 2 N

Monobromoacetic acid 79-08-3 1938 138.94802 C 2 H 3 BrO 2

4.1.3 Other chemicals

Component Chemical Name CAS Number UN Number Molecular Weight (g/mol) Empirical formula Nitrogen gas 7727-37-9 1066 28.013 N 2

4.1.4 Structural formula

Hypochlorous acid Hydrogen peroxide Ozone Chlorine dioxide Bromoform Dibromo chloromethane

Dichlorobromomethane 2, 4, 6 ñ Tribromophenol Dibromo acetonitrile Monobromoacetic acid Nitrogen

gasMEPC 57/2/6 ANNEX Page 25

I:\MEPC\57\2-6.doc 4.2 Physical and chemical properties for th e Actives Substances and Preparations and treated ballast water

Available data describing the properties of the chemicals is highly variable and when sufficient data have not been obtainable, the chemical is not presented.

4.2.1 Active Substances

Property Hypochlorous acid Sodium hypochlorite Hydrogen peroxide Ozone Chlorine dioxide

Melting point (  ̊ C) - -25 -33 35% w/w in

water -526.5

-59 Boiling point (  ̊ C) - 107 108 at 1013 hPa 35% w/w in

water -112 o C

11 Flash point (  ̊ C) - N/A Density kg/m 3 at 20  ̊ C - 1.21g/cm 3 1.1-1.2 35% w/w in

water 2.144g/L (0 o C) 1.01g/cm 3 (4 o C)

Vapour pressure at 20  ̊ C - 17.4-20 hPa 0.48 hPa at 30°C 41257 mm Hg (-12 o C) 1420 hPa

Vapour density (air = 1) - - - - 2,3 Water solubility (g/L) Soluble 293 100% miscibility at any ratio 7.5 g/L

pH in solution - - - - 2-3 (8g/L) Dissociation constant (pKa) 7.5 - - - -

Octanol/water partition coefficient (log K ow ) -0.87 -3.42 -0.296 - -

Corrosivity to material or equipment - - Reacts with rust, brass, zinc, nickel, copper, iron and their alloys - -

Explosive properties - - Vapor in equilibrium with aqueous solutions above 70% by weight can explode - Explosive with or without

contact with air

Oxidizing properties - One of the

more commonly used oxidizing agent Classified as oxidizing agent for transport - Strong oxidizing agentMEPC 57/2/6 ANNEX Page 26

I:\MEPC\57\2-6.doc 4.2.2 Relevant Chemicals

Property Bromo form Dibromochlor omethane Bromodichlor o-methane 2,4,6 - Tribromoph enol Dibromo acetonitrile Bromo acetic acid Melting point (  ̊ C) 8.0-8.5 -20 -55 93 67 49

Boiling point (  ̊ C) 149.5 119-120 87 at 760 mm Hg 290 at 994,58 hPa 67 at 24.0 mm Hg 206

Flammability (  ̊ C) N/A - - nonflammable. >93 -

Density 2.89 - - 2.55 - -

Vapour pressure at 20  ̊ C 667 5.54 mm Hg 50.0 mm Hg - 2.0 mm Hg at 50°C ; 15 mm Hg at 70°C; 48 mm Hg at 95°C -

Vapour density (air = 1) 8.72 (calculate d) 2.451 - - - -

Water solubility Slight 0.4 g/100 mL 5-10 mg/mL at 19°C 50 mg/mL at 20 °C 5-10 mg/mL at 21.5°C miscible

Octanol/water partition coefficient (log K ow ) 0.38 2,08 1,88 4,02 N/A 0.295

Dissociation constant pKa 2.06 2.16 - - - -

Corrosivity to material or equipment Not corrosive - - - - -MEPC 57/2/6 ANNEX Page 27

I:\MEPC\57\2-6.doc 4.3 Data on environmental fate and eff ects under aerobic and anaerobic conditions

4.3.1 Modes of degradation

4.3.1.1 Bromoform

In air, brominated trihalomethanes (THMs) may be degraded by photo-oxidative interaction with atmospheric hydroxyl radicals; their typical atmospheric ha lf-life is about 2 months

.

The main route of loss of THMs from the water phase has been reported to be through volatilization, with a recorded volatilization half-life rang ing from 0.5 hours to 24 days. (WHO 1996, Taylor 2006). The reported biodegrada tion half-life under aerobic conditions has been reported to around 1 m onth (Taylor, 2006). Under anae robic conditions, brominated trihalomethanes are readily bio-degraded within days in the presence of methane-producing bacteria and under denitrifying an d sulphate-reducing conditions (Taylor, 1996). Adsorption to suspended matter and abiotic degradation (e.g. vi a hydrolysis) have been reported as negligible (Taylor, 2006); The estimated ha lf-life through hydrolys is in aqueous media is 686 years for bromoform (WHO, 1996).

During experiments in open (air exposed), reaction vessels (150 li tres) concentrations of THMs in chlorinated seawater decreased from 15 lg/L to <0.25 lg/L over 7 days. (In closed reaction vessels, only a small decrease of THMs in chlori nated water was observed .) The following first order rate constant (k) and half-life (t0.5) were determined for Bromoform: total loss: k = 0.027, h_1 t0.5 = 26 h; net volatilization loss: k = 0.024, h_1 t0.5 = 28 h.

The potential toxicity (pT) of open vessels of chlorinated seawat er declined to non-chlorinated intake levels within 2 ñ 3 days. Thereafter, th e pT remained relatively constant. In a closed system, no significant decrease in pT was observed. Although samples were tested for genotoxicity, the resu lts were equivocal ñ local inputs, probably from ot her industrial activities, were sufficient to mask any influence of low-level chlori nation (Taylor 2006)

Bromoform should be regarded relatively pers istent once released into the environment (also stated in GESAMP-B WWG 3/9 (MEPC 56/2/2)).

4.3.1.2 Dibromochloromethane

(As for Bromoform; THMs in general.)

In Taylor (2006), the following firs t order rate constant (k) and ha lf-live (t0.5) were determined for DBCM (in seawater): total loss: k = 0.040, h _1 t0.5 = 17 h; net volatilization loss: k = 0.031, h_1 t0.5 = 22 h.

Adsorption to suspended matter and abiotic degrada tion (e.g. via hydrolysis) has been reported as negligible (Taylor, 2006); esti mated half-live through hydrolysis in aqueous media is 274 years for DBCM (WHO, 1996) (see also MEPC 56/2) , thus DBCM should be regarded relatively persistent once released into the environment.MEPC 57/2/6 ANNEX Page 28

I:\MEPC\57\2-6.doc 4.3.1.3 Dichlorobromomethane

(As for Bromoform; THMs in general.)

In Taylor (2006), the following first order rate cons tant (k) and half-life (t0.5) were determined for DCBM (in seawater): total loss: k = 0.080 h_1 t0.5 = 9 h.

Adsorption to suspended matter and abiotic degrada tion (e.g. via hydrolysis) has been reported as negligible (Taylor, 200 6); estimated half-life through hydrolysis in aqueous media is 1000 years for DCBM (WHO, 1996), thus DCBM should be rega rded relatively persistent once released into the environment.

4.3.1.4 Tribromophenol

Halophenols have been known to be partially i onised at ambient pH va lues. The volatilization half-lifes of 2,4-dichlorophenol and 2,4,6-trichlorophenol have been reported as 2 weeks. Halophenols have been known to be susceptib le to photodegradation and this has been understood to be the major fate process, with a half-life of several days (Taylor, 2006). Volatilization of non-dissociated 2,4,6-TBP from water surfaces is not expected to be an important fate process (Dan ske Milj ̄ministeriet, 2000).

Tribromophenol is not regarded as readily biodegradable (49% of BOD, 4w, 100 mg/L substance, 30 mg/L sludge) (Danske Milj ̄mini steriet, 2000), however, adapted communities of micro-organisms and specialist communities (such as anaerobic or sulfidogenic) may degrade the compounds (WHO 2005). Biodegradati on half-lifes have been repor ted as being 7 days and the degree of adsorption to suspende d solids and sediments (and biocon centration) has been reported as moderate (Taylor, 2006, WHO 2005).

4.3.1.5 Dibromoacetonitrile

The half-lifes of dihaloacetonitr iles such as dibromoacetonitrile (DBAN) have been reported as being of the order of several days, dependent on pH, with the primary route being gradual hydrolysis into dihalolacetic acids. Adsorption to solids has been reported as negligible (Taylor, 2006).

In Taylor (2006) for both open and closed reacti on vessels (seawater), >90% dibromoacetonitrile was lost in 40 h giving k = 0.050, h _1 t0.5 = 14 h. The potential toxi city (pT) of open vessels of chlorinated seawater declined to non-chlorinated intake levels within 2ñ3 days. Thereafter the pT remained relatively constant. In a closed sy stem no significant decrease in pT was observed. Although samples were tested for genotoxicity the results were equivocal: local inputs, probably from other industrial activities, were sufficient to mask any influence of low-level chlorination (Taylor, 2006).MEPC 57/2/6 ANNEX Page 29

I:\MEPC\57\2-6.doc 4.3.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient

4.3.2.1 Hypochlorous acid

Results Log Kow -0.87 hypochlorous acid -3.42 sodium hypochlorite Koc 14.3 hypochlorous acid 14.3 sodium hypochlorite 1⁄2-life 0.8 h hypochlorous acid 1.4 h sodium hypochlorite

Hypochlorous acid and sodium hypochlorite can not be considered as bioaccumulative based on given data.

As the log K ow values for sodium hypochlorite and hy pochlorous acid are very low, it is considered unlikely that these substances should accumulate through the food chain.

4.3.2.2 Hydrogen peroxide

Results Reference Log K ow H 2 O 2 does not accumulate in cells of living organisms IUCLID 2000

4.3.2.3 Bromoform

Bromoform may be slightly bioconcentrated by aquatic organisms, though the octanol/water partition coefficient (Kow) is 2.38, which is smaller than the rough indication value for bioaccumulation potential of Log Kow > 3). The chemical may in case of bioaccumulation tend to partition to fat tissues of aquatic organisms (WHO, 1996).

As described in Taylor (2006) for coastal and estuarine power stationí s cooling water, the influence of long-term exposure by chlorinatio n residues (including bromoform) on sea bass ( Dicentrarchus labrax ) was found to be very limited. Although some bioaccumulation of bromoform was noted during annual chlorination seasons, this accumulation rapidly dissipated thereafter. No impacts on growth were observed and no damage to liver tissues was observed.

4.3.2.4 Dibromochloromethane

DBCM may be faintly bioconcentrated by a quatic organisms, although the octanol/water partition coefficient (Kow) is 2.08, which is smaller than the rough indication value for bioaccumulation potential of Log K ow > 3. The chemical may in case of bioaccumulation tend to partition to fat tissues of aquatic organisms (WHO, 1996).

As described in Taylor (2006) for coastal and estuarine power stationí s cooling water, the influence of long-term exposure by chlorinatio n residues (including bromoform) on sea bass ( Dicentrarchus labrax ) was found to be very limite d. Although some bromoform bioaccumulation was noted during annual chlorination seasons, this accumulation rapidly dissipated thereafter. No impact s on growth were observed and no damage to liver tissues.MEPC 57/2/6 ANNEX Page 30

I:\MEPC\57\2-6.doc 4.3.2.5 Dichlorobromomethane

DCBM may be faintly bioconcentrated by a quatic organisms, although the octanol/water partition coefficient (Kow) is 1.88, which is well below the rough indication value for bioaccumulation potential of Log Kow > 3. It is suggested that the chemical in case of bioaccumulation will tend to partition to fa t tissues of aquatic organisms (WHO, 1996).

As described in Taylor (2006) for coastal and estuarine power stationí s cooling water, the influence of long-term exposure by chlorinatio n residues (including bromoform) on sea bass ( Dicentrarchus labrax ) was found to be very limite d. Although some bromoform bioaccumulation was noted during annual chlorination seasons, this accumulation rapidly dissipated thereafter. No impact s on growth were observed and no damage to liver tissues.

4.3.2.6 2,4,6-Tribromophenol

Measured values suggest that the potential for bioconcentra tion of 2,4,6-TBP in aquatic organisms is moderate to high. Octanol/wat er partition coefficien t (log Kow) is 4.02.

Exposure of bluegills ( Lepomis macrochirus ) to 14C-labelled 2,4,6- TBP for 28 days resulted in 20-fold bioaccumulation in edible tissue and 140-fold bioconcentration in viscera. Plateau levels were reached by 3 ñ 7 days of exposure. The half-life for residues was less than 24 h following termination of exposure (WHO 2005).

As described in Taylor (2006) for coastal and estuarine power stations cooling water, the influence of long-term exposur e by chlorination residues (inc luding 2,4,6-Tribromophenol) on sea bass ( Dicentrarchus labrax ) was found to be very lim ited. Although some bromoform bioaccumulation was noted during annual chlorination seasons, this accumulation rapidly dissipated thereafter. No impact s on growth were observed and no damage to liver tissues.

4.3.2.7 Dibromoacetonitrile

Adsorption to sediment and bioconcentration in aquatic organisms is stated in WHO (2004) as ìnot expectedî.

As described in Taylor (2006) for coastal and estuarine power stations cooling water, the influence of long-term exposure by chlorination residues (including Dibromoacetonitrile) on sea bass ( Dicentrarchus labrax ) was found to be very limited. Although some bromoform bioaccumulation was noted during annual chlorination seasons, this accumulation rapidly dissipated thereafter. No impact s on growth were observed and no damage to liver tissues.

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

4.3.3.1 Bromoform

BDCM is metabolized to phosgene, whereas DBCM and bromoform are metabolized to brominated analogues of phosgene. The rate of metabolism of thes e compounds to carbon monoxide both in vivo and in vitro generally follows the halide order: namely, bromoform >> DBCM > BDCM >> chloroform. IPCS (2000) postulated that the brominated THMs may be more rapidly and more extensivel y metabolized than their chlori nated counterparts. Although thisMEPC 57/2/6 ANNEX Page 31

I:\MEPC\57\2-6.doc may be true for BDCM, support for this statement, as it pertains to DBCM or bromoform, is difficult to determine from the limited literature currently available. The majority of the comparative metabolism studies conducted to date are limited to chloroform or BDCM. Nonetheless, it would appear that the toxicity of BDCM and lik ely other brominated THMs is mediated through a bioactiva tion pathway (from WHO 2005).

No information on persistence of metabolites has been found.

4.3.3.2 Dibromochloromethane

See description for bromoform.

According to MEPC 56/2, no persistent substance is formed.

4.3.3.3 Dichlorobromomethane

See description for bromoform.

No information on persistence of metabolites has been found.

4.3.3.4 2,4,6-Tribromophenol

TBP is in itself a natural metabolite from infauna in marine pristine soft bottom habitats (for example from Acorn worms (enteropneusta )). However, no information was found on the metabolites of TBP (same conclusion in WHO 2005).

4.3.3.5 Dibromoacetonitrile

Halogenated acetonitriles are metabolized via oxidative de halogenation and dehydration to carbon dioxide and cyanide, which is then further metabolized to thiocyanat e. The first step in this reaction is catalysed by a mixed-function ox idase (such as a cytoch rome P-450) and results in production of a halocyanomethanol. It is prop osed that the halocyanomethanols then dehydrate to form halocyanoformaldehydes or lose cy anide to form haloformaldehydes, including phosgene. The cyanide carbon group is more read ily excreted in the urine, whereas the halomethyl carbon group is excreted nearly equally in expired air and in urine; excretion in faeces is low (WHO 2004).

Data on persistence of main me tabolites have not been found.

4.3.4 Reaction with organic matter

4.3.4.1 Bromoform

When chlorine or bromine is used to treat balla st water, trihalomethanes such as bromoform are formed as a by-product. They result from the re action of chlorine and/or bromine with organic matter in the water being treated. However, once the bromoform is formed, it does not appear to have any further reactions with organic matter (MEPC 56/2/3).MEPC 57/2/6 ANNEX Page 32

I:\MEPC\57\2-6.doc 4.3.4.2 Dibromochloromethane

When chlorine or bromine is used to treat ballast water, THMs ar e formed as a by-product. They result from the reaction of chlori ne and/or bromine with organic matter in the water being treated. However, once the THM is formed it does not app ear to have any further reactions with organic

matter.

4.3.4.3 Dichlorobromomethane

When chlorine or bromine is used to treat ballast water, THMs ar e formed as a by-product. They result from the reaction of chlori ne and/or bromine with organic matter in the water being treated. However, once the THM is formed, it does not appear to have any further reactions with organic

matter.

4.3.4.4 2,4,6-Tribromophenol

Bromophenols can be formed during the chlorinati on of natural water and wastewater containing phenol and bromide ions. No information has been found on further reactions with organic

matter.

4.3.5 Potential physical effects on wildlife and benthic habitats

4.3.5.1 Bromoform

No information is available on the effects on wildlife or benthic ha bitats (MEPC 56/2/3), however, significant physical eff ects have not been considered relevant for this substance.

4.3.5.2 Dibromochloromethane

DBCM has a higher specific gravity than seawater (2.451 (20°C)) and a low solubility (2.7g/L (20°C)). Therefore, according to evaluation based on GE SAMP hazard evaluation (GESAMP (2002)), the compound is classified as Rating S (substances having a potential effect on benthic habitats) (MEPC 56/2).

4.3.5.3 Dichlorobromomethane

No information has been available on physical ef fects on wildlife and benthic habitats, however, significant physical effects ha ve not been considered rele vant for this substance.

4.3.5.4 2,4,6-Tribromophenol

No information has been available on physical ef fects on wildlife and benthic habitats, however, significant physical effects ha ve not been considered rele vant for this substance.

4.3.6 Potential residues in seafood

4.3.6.1 Bromoform

No information has been found on bromoform residues in seafood (see also MEPC 56/2/3).MEPC 57/2/6 ANNEX Page 33

I:\MEPC\57\2-6.doc 4.3.6.2 Dibromochloromethane

As DBCM is considered to have low bioaccumu lation potential, its persistence in seafood is expected to be low. According to studies, DB CM was not detected in oysters, clam and the sediment of the Ariho River and the Yoshinaga River (MEPC 56/2).

4.3.6.3 Dichlorobromomethane

DBCM is not a common food contaminant but has been found in trace amounts in some samples: 1.2 μg/kg in one dairy composite and 7 μg/kg in butter (WHO, 1996). However, information on potential residues in seafood has not been found.

4.3.6.4 2,4,6-Tribromophenol

2, 4, 6-tribromophenol has been measured in w ild-harvested prawns and ocean fish in Eastern Australia. The levels ranged from 0.1 to 230 ng/g in fish (gut, flesh) and 0.12-460 ng/g in prawns (head, tail) (Danske Milj ̄m inisteriet, 2000). In biota likely to form part of huma n diets, edible portions contain mean 2,4,6-TBP concentrati ons up to 198 and 2360 μg/kg dry weight in molluscs and crustaceans, respectively, and up to 39 μg/kg dry weight in marine fish. Brominated phenols have been detected in human m ilk, blood, and adipose tissue (WHO 2005).

4.3.7 Interactive effects

No information has been f ound on interactive effects.

4.4 Effects on aquatic plants, invertebrates, fish and other biota

The Active Substances are added to eliminate organisms present afte r the initial physical treatment (i. e. filtration) of the ballast water. However, when added to the ballast-water, new compounds might be formed in reaction with th e Active Substances. The toxicity of these compounds is of importance to the crew on the sh ip and to the environment where the ballast water is expelled. The toxicity of an Active S ubstance is not definite; it acts differently on different organisms, resu lting in a variety of LC 50 (Lethal Concentr ation for 50%), EC 50 (Effective Concentration for 50%), NOEC (No Eff ect Concentration) and LOEC (Lowest Effect Concentration) values. The lowest L C 50 , E C 50 , NOEC and LOEC for eac h species are prese n ted below. Preferably, there are to xicological data on th ree taxonomic groups (i.e. algae, fish and crustacean), with endpoints on reproduction or gr owth. Mortality data does not give any good estimation for persistence or bioa ccumulation, but is anyhow presen ted together with short- and long-term effect data, which together compre hends a fuller picture on the kinetics of the substance.

The ecotoxicological data presented below is not to be considered as complete and only substances where relevant data has been availa ble are presented. (IUP AC names derived from www.ebi.ac.uk/chebi/init.do and UN numbers derived from http://cameochemicals.noaa.gov/ ).MEPC 57/2/6 ANNEX Page 34

I:\MEPC\57\2-6.doc The toxicological data is derive d from the following databases:

http://cfpub.epa.gov/eco tox/advanced_query.htm

, http://ecb.jrc.it/esis/

, http://cameochemicals.noaa.gov/ search?action=new&type=simple http://www.ebi.ac.uk/chebi/init.do http://toxnet.nlm.nih.gov/

To further investigate the toxici ty of the anolyte from the OS BWMS, an ecotoxicology search of the internal Active Substances and Relevant Ch emicals has been performed. Ecotoxicological data has not been found for all substances, and not all data ca n be considered relevant for estimating the short- and long-term effects. N/ a indicates that suffici ent data has not been available.

4.4.1 Hypochlorous acid

4.4.1.1 Fish

Effect Species End point Reference Acute aquatic toxicology Oncorhynchus kisutch , Coho salmon LC 50 : 32 μ g/L/4 days Thatcher 1978

Chronic aquatic toxicity Oncorhynchus gorbuscha, Pink salmon NOEC: 42 μ g/L/23 days, mortality Holland et al 1960

4.4.1.2 Crustacean

Effect Species End point Reference Acartia tonsa, Calanoid

copepop LC 50 : 403 μ g/L/1 day Bradley et al 1997 Acute aquatic toxicology Americamysis bahia, Opossum shrimp LC 50 : 143.6 μ g/L/ 7 days Fischer et al 1994

Americamysis bahia

, Opossum shrimp NOEC: 47.8 μ g/L/ 7 days, reproduction Fischer et al 1994

Americamysis bahia

, Opossum shrimp NOEC: 65.5 μ g/L/ 7 days, development Fischer et al 1994 Chronic aquatic toxicity

Americamysis bahia

, Opossum shrimp NOEC: 81.2 μ g/L/ 7 days, growth Fischer et al 1994

4.4.1.3 Algae

Effect Species End point Reference Chronic aquatic toxicity Porphyra yezoensis , Red algae EC 50 : 1400 μ g/L/ 10 days, growth Maruyama et al 1988MEPC 57/2/6 ANNEX Page 35

I:\MEPC\57\2-6.doc 4.4.2 Hydrogen peroxide

4.4.2.1 Fish

Effect Species End point Reference Oncorhynchus mykiss

, Rainbow trout LC 50 : 10 000 μ g/L/ 4 days Office of Pesticide Programs, 2000 Acute aquatic toxicology Lepomis macrochirus, Bluegill LC 50 : 18 000 μ g/L/ 4 days Office of Pesticide Programs, 2000

4.4.2.2 Crustacean

Effect Species End point Reference Chronic aquatic toxicity Americamysis bahia, Opossum shrimp LC 50 : 47.8 μ g/L/ 7 days, reproduction Fischer et al 1994

4.4.2.3 Algae

Effect Species End point Reference

Acute aquatic toxicology Alexandrium tamarense, Dinoflagellate LC 50 : 10 000-50 000 μ g/L/0-3 days, reproductionGermination Ichikawa, S, Wakao, Y, Fukuyo, Y. 1993 Chronic aquatic toxicity Porphyra yezoensis, Red algae LC 50 : 1400 μ g/L/10 days, growth Maruyama, T et al 1988

4.4.3 Ozone

4.4.3.1 Fish

Effect Species End point Reference

Lepomis macrochirus, Bluegill LC 50 : 60 μ g/L/24hr Paller & Heidinger 1979 Morone saxatilis, Striped bass LC 50 : 150 μ g/L/6hr Hall et al 1981 Pimephales promelas, Fathead minnow LC 50 : 100 μ g/L/0.03hr Asbury & Coler 1980 Salmo gairdneri, Rainbow

trout LC 50 : 9.3 μ g/L/96 hr Wedemaier et al 1979

Perca flavescens, Yellow perch LC 50 : 210 μ g/L/24hr/embryo Coler & Asbury 1980 Acute aquatic toxicology

Salmo gairdneri, Rainbow

trout LC 50 : 190-310 μ g/L/ embryoMEPC 57/2/6 ANNEX Page 36

I:\MEPC\57\2-6.doc 4.4.3.2 Crustacean

No sufficient data available.

4.4.3.3 Algae

No sufficient data available.

4.4.4 Chlorine dioxide

4.4.4.1 Fish

Effect Species End point Reference Salmo trutta , Brown

trout LC 50 : 10 000 000 μ g/L/48hrs Woodiwiss, FS, Fretwell, G. 1974 Acute aquatic toxicology Rasbora heteromorpha

, Harlequinfish, red rasbora LC 50 : 7 000 000 μ g/L/24hrs Tooby, TE, Hursey, PA, Alabaster, JS. 1975

4.4.4.2 Crustacean

Effect Species End point Reference Carcinus maenas , Green / European shore crab LC 50 : 500 000 μ g/L/48hrs Portmann, JE, Wilson, KW, 1971 Acute aquatic toxicology Crangon crangon , Common shrimp LC 50 : 500 000 μ g/L/48hrs Portmann, JE, Wilson, KW, 1971

4.4.4.3 Algae

Effect Species End point Reference Acute aquatic toxicology Macrocystis pyrifera, Giant kelp LC 50 : 2500 μ g/L/48hrs Hose, JE, Fiore Di, D, Parker, HS, Sciarrotta, T. 1989

4.4.5 Bromoform

4.4.5.1 Fish

Effect Species End point Reference Cyprinodon variegates, Sheapshead minnow NOEC: 2900 μ g/L/ 4 days Heitmuller PT. et al 1981 Cyprinodon variegates, Sheapshead minnow LC 50 : 18000 μ g/L/96hrs

Lepomis macrochirus

, Bluegill LC 50 : 29000 μ g/L/96hrs Boccafusco et al . 1981 Acute aquatic toxicology

Oryzias latipes, Japanese killifish/Medaka LC 50 : 40400 μ g/L/48hrs MITI 1992

Chronic aquatic toxicity Cyprinodon variegatus, Sheepshead minnow LC 50 : >4800<8500 μ g/L/> 28 days, Mortality, Maximum acceptable Toxicant Concentration Ward, GS. Parrish, PR, Rigby, RA, 1981MEPC 57/2/6 ANNEX Page 37

I:\MEPC\57\2-6.doc 4.4.5.2 Crustacean

Effect Species End point Reference Penaeus aztecus

, Brown shrimp LC 50 : 20 000 μ g/L/4 days Gibson, CI. et al 1981 Acute aquatic toxicology Daphnia magna, Water flea LC 50 : 46 000 μ g/L/48hrs LeBlanc 1980

Daphnia magna, Water flea EC 50 : 5400 μ g/L/15days, reproduction Canton, JH. et al 1983 Chronic aquatic toxicity Penaeus aztecus, Brown shrimp LC 50 : 30-290 μ g/L 1-28days, accumulation, general Gibson, CI. et al 1981

4.4.5.3 Algae

Effect Species End point Reference Selenastrum capricornutum, Green algae LC 50 : 18,7 μ g/L/24hrs Chlorophyll US EPA 1978 Acute aquatic toxicology

Selenastrum capricornutum, Green algae LC 50 : 28,1 μ g/L/96hrs Population changes, general US EPA 1978

4.4.6 Dibromochloromethane

4.4.6.1 Fish

Effect Species End point Reference Acute aquatic toxicology Cyprinus carpio

, Common camp LC 50 : 52 000 μ g/L/ 45 min Mattie, JS. et al 1981

4.4.6.2 Crustacean

No sufficient data available.

4.4.6.3 Algae

No sufficient data available.

4.4.7 Dichlorobromomethane

4.4.7.1 Fish

No sufficient data available.

4.4.7.2 Crustacean

No sufficient data available.MEPC 57/2/6 ANNEX Page 38

I:\MEPC\57\2-6.doc 4.4.7.3 Algae

No sufficient data available.

4.4.8 2,4,6-Tribromophenol

4.4.8.1 Fish

Effect Species End point Reference Pimephales promelas

, Feathered minnow LC 50 : 6250 μ g/L/96hrs, Broderius, SJ, Kahl, MD, Hoglund, MD, 1995 Pimephales promelas

, Feathered minnow LC 50 : 6540 μ g/L/96hrs Geiger, DL, Northcott, CE, Call, DJ, Brooke, LT. 1985 Acute aquatic toxicology

Pimephales promelas

, Feathered minnow LC 50 : 4500 μ g/L/ 8 days Phipps, GL. et al 1981

4.4.8.2 Crustacean

Effect Species End point Reference Acute aquatic toxicology Daphnia magna Water flea LC 50 : 1290 μ g/L / 2 days, Carlson, R. M, Caple, R. 1977

4.4.8.3 Algae

Effect Species End point Reference Acute aquatic toxicology Bacillariophyceae

, Diatom LC 50 : 500 μ g/L/48hrs, Physiology Erickson, SJ, Hawkins, CE, 1980

Chronic aquatic toxicity Thalassiosira pseudonana, Diatom LC 50 : 16 000 μ g/L/7days, population changes, general Erickson, SJ, Freeman, AE, 1978

4.4.9 Dibromoacetonitrile

4.4.9.1 Fish

Effect Species End point Reference Acute aquatic toxicology Pimephales promelas, Feathered minnow LC 50 : 710 μ g/L/24hrs 550 μ g/L/96hrs Mayes, MA, Blanchard FA, Hopkins, DL, Takahashi, IT, 1985

4.4.9.2 Crustacean

Insufficient data available.MEPC 57/2/6 ANNEX Page 39

I:\MEPC\57\2-6.doc 4.4.9.3 Algae

Effect Species End point Reference Glenodinium halli, Dinoflagellate LC 50 : 16 000 μ g/L/7days, Population changes, general Erickson, SJ, Freeman, AE, 1978 Chronic aquatic toxicity

Scenedesmus subspicatus, Green algae EC 50 : 1400 μ g/L/72hrs, (Population changes, general) Kuhn, R, Pattard, M, 1990

4.4.10 Monobromoacetic acid

4.4.10.1 Fish

Effect Species End point Reference Cyprinus carpio

, Common carp LC 50 : 326mg/kg (100% mortality after 1.5hrs, force-fed), 222mg/kg LT100 (100% mortality after 5hrs, force-fed) Loeb, HA, Kelly, WH, 1963 Acute aquatic toxicology

Lepomis macrochirus

, Bluegill LC 50 : 5ppm/24hrs (Solvents: Ethanol, 2- Propanone, Multiple effects reported as one result) Applegate, VC, Howell, JH, Hall Jr. AE, Smith, MA, 1957

4.4.10.2 Crustacean

Effect Species End point Reference Acute aquatic toxicology Daphnia magna, Water flea EC 50 : 65 000 μ g/L/24hrs, behavior- equilibrium, intoxication-immobile) Kuhn, R. 1988, Kuhn, R. Pattard, M, Pernak K-D, Winter, A, 1989 Chronic aquatic toxicity Daphnia magna, Water flea NOEC: 1600 μ g/L/21 days, Reproduction Kuhn, R. et al 1989

4.4.10.3 Algae

Effect Species End point Reference Chronic aquatic toxicity Monoraphidium griffithii, Green algae EC 50 : 60 μ g/L/4 days, growth Eloranta, V 1982MEPC 57/2/6 ANNEX Page 40

I:\MEPC\57\2-6.doc 4.5 Data on mammalian toxicity

4.5.1 Hypochlorous acid

4.5.1.1 Effects on skin and eye

Exp. route Species Method Results Reference Skin Rabbit OECD 404 2% slight 20% severe Sodium hypochlorite,IUCLID 2000; GESAMPBWWG 3/9 (MEPC 56/2/2) Eye Rabbit n/a 5.25% irritant 0.5% slight irritant 0.05% NOEC Sodium hypochlorite,IUCLID 2000; GESAMPBWWG 3/9 (MEPC 56/2/2)

4.5.1.2 Corrosion/irritation

Exp route Exp duration Exp dose Species NOAEL Reference

Oral 90 days 200 mg/L in drinking water Sodium hypochlorite Mouse 50mg/L (10-12 mg/kg/day) MEPC 56/2, paragraph 2.3.3.1 (Daniel et al 1991)

4.5.1.3 Sensitization data

Exp route Species Method Results Reference Skin Guinea pig n/a 2.8% NOEC Sodium hypochlorite, IUCLID 2000; GESAMP-BWWG 3/9 (MEPC 56/2/2)

4.5.1.4 Developmental and reproductive toxicity

Exp route Exp duration Exp dose Species NOAEL Reference Oral 7 generations 100 mg sodium hypochlorite/L Rats 100 mg/L GESAMP - BWWG

4.5.1.5 Carcinogenicity

Effect Species Method Results Reference Carcinogenicity Not carcinogetic GESAMP0-BWWG MEPC 56/2, paragraph 2.3.7.1 Mutagenicity Not mutagenic GESAMP- BWWG MEPC 56/2, paragraph 2.3.7.1MEPC 57/2/6 ANNEX Page 41

I:\MEPC\57\2-6.doc 4.5.2 Hydrogen peroxide

Source: EU-risk assessment report ñ Hydrogen Peroxide.

4.5.2.1 Effects on skin and eye

Exp route Species Method Results Reference Skin Rat Whole body, 4 hours LC 50 : 2000 mg/m 3 Kondrashov 1977 Eye Mouse Aerosols (70% H 2 O 2 ) 19000-9400 mg/m 3

, 30 min Gross opacies, microscopic eye lesions Punte et al 1953

Inhalation Mouse Aerosols (70% H 2 O 2 ), 5 min -2 hrs, exp at 12000- 13000 mg/m 3 50% lethality after 10-15 min Punte et al 1953

4.5.2.2 Corrosion/irritation

Exp
route Exp duration Exp dose Species Method Results NOAEL NOE L Reference

Inhalation 28 days 0-33 mg/

m 3 Rat 6 hrs daily for 5 days per week Respiratory tract irritation, necrosis and inflammation of nasal cavity epithelium 2.9 mg/m 3 14.6 mg/

m 3 CEFIC Peroxygen Sector Group 2002

Oral 12 weeks 0- 506 mg/k

g bw/d Rat Stomach tube 6 days per week Decreased bw gain, erythrocyte count, hemoglobin conc. Gastric mucosal erosions, eschars and round cell infiltration 56.2

mg /kg bw/d Ito et al

1976

Oral 0-90 days 0- 3000

ppm Mouse Drinking

water Decreased bw gain, reduced blood total protein, reduced food and water consumption, duodenal mucosal hyperplasia 100

ppm 300

ppm FMC 1997MEPC 57/2/6 ANNEX Page 42

I:\MEPC\57\2-6.doc 4.5.2.3 Sensitization

Exp route Species Method Results Reference Skin Human Vapour, 5 min-4 hr

exposure NOAEL: 10 mg/m 3 , Effect conc/dose: 20 mg/m 3 Kondrashov 1977 Inhalation Human Face mask (nose inhalation) NOAEL: 5 mg/m 3 , Effect conc/dose: 10 mg/m 3 Kondrashov 1977

4.5.2.4 Developmental and reproductive toxicity

Exp route Exp duration Species Method Results Reference Oral 90 days Mouse Drinking

water No effects FMC 1997

4.5.2.5 Carcinogenicity

Species Method Results Reference Mouse Drinking water Increased incidence of erosions and ulcer in the glandular stomach and duodenal hyperplasia Ito et al 1981a, Ito et al 1982b Hamster Painting of left buccal pouch twice weekly with DMBA* and H 2 O 2 Development of carcinomas, hyperkeratosis and hyperplasia Weitzman et al 1986

Mouse Dermal, treatment on dorsal skin with DMB*A and H 2 O 2 and/or acetone twice weekly H 2 O 2 functioned as an extremely weak tumor promoter KleinSzanto and Slaga 1982

*9,10-dimethyl-1,2-bentzanthraceneMEPC 57/2/6 ANNEX Page 43

I:\MEPC\57\2-6.doc 4.5.2.6 Mutagenicity/genotoxicity

Species Strain Measured endpoint Test conditions Results without activation Results with activation Reference

Escherichia coli WP2 (uvrA) Ames test H 2 O 2 , 1.0- 3333.3 μ g/pla

te - - SRI International 1980 Salmonella typhimurium TA1535/pS K1002 DNA damage and repair H 2 O 2 , 45 μ g/ml + NT Nakamura et al 1987 African green monkey Kidney cells (CV-1) Mammalian cell-line mutation ñ (supF locus of the pZ189 plasmid mutations) H 2 O 2 , 0.5- 10mM + NT Moraes et al 1990

Chineese hamster V79-379A cells DNA damage and repairñ DNA singleand doublestrand breaks H 2 O 2 , 10- 1000 μ M + NT Prise et al 1989

4.5.3 Ozone

4.5.3.1 Corrosion/Irritation

Exp route Species Method Results Reference Oral Human Inhalation 0.021-0.124 ppm/29 min Decremented FVC, FEV 1 , PEFR Spektor et al 1988

Oral Human Inhalation 0.08ppm/6.6hrs Decremented FVC, FEV 1 Increased SRaw McDonnell et al 1991

4.5.3.2 Repeated-dose toxicity

Exp duration Exp dose Species Results Reference

8 hrs/day day 6-9, 9-12 and 6-15 of gestation 1.97

ppm Rat Increased resorption rate Kavlock et al 1979

day 17-20 of gestation 1.0 or 1.5

ppm Rat Offspring with retarded of reflex development and slowing in open field behaviour Kavlock et al 1980MEPC 57/2/6 ANNEX Page 44

I:\MEPC\57\2-6.doc 4.5.3.3 Developmental and reproductive toxicity

Exp duration Exp dose Species Method Results Reference

Day 17-20 of gestation 2 and 2.9 mg/m 3 Rat (offspring) Maternal

exposure Retarded reflex development, slowing open field behaviour Kavlock et al 1980

7hrs/day, 5 days/week 0.4 mg/m 3 Mouse (fetus) Maternal

exposure Blepharophimosis and jaw anomalies Veninga 1967 6 hrs 2 mg/m 3 Rat (pregnant/ lactating) Enhanced sensitivity to o3 pulmonary inflammation Gunnison et al 1992

4.5.3.4 Carcinogenicity

Ozone is not considered as carcinogenic (The American Conference of Governmental Industrial Hygienists (ACGIH)).

4.5.4 Chlorine dioxide

Very limited data available, probably due to the f act that chlorine dioxide is readily decomposed to chlorine and oxygen in the environment.

4.5.4.1 Acute toxicity

Species Exp route Type Value Reference Rat Oral LD 50 292 mg/kg bw Finnish Chemicals Oy ƒets‰ Rat Inhalation LCLo 500 ppm Finnish Chemicals Oy ƒets‰

4.5.4.2 Skin and eye irritation

Organ Species Remark Reference Skin Human May irritate skin very slightly Finnish Chemicals Oy ƒets‰ Eye Human Vapours may irritate eyes Finnish Chemicals Oy ƒets‰

4.5.4.3 Carcinogenicity

Chlorine dioxide is not classified car cinogenic (Finnish Chemicals Oy ƒets‰).

4.5.5 Bromoform

4.5.5.1 Acute toxicity

Exp route Value Species Reference/comments Oral LD 50 (mg/L) 707-1550 Rats & Mice EHC 216, 2000; GESAMP-BWWG Inhalation LC 50 (mg/L/4h) 7000 μ /L Dogs Death after 1h GESAMP- BWWGMEPC 57/2/6 ANNEX Page 45

I:\MEPC\57\2-6.doc 4.5.5.2 Repeated dose toxicity

Exp route Exp duration Exp dose Species NOAEL Reference

Oral 13 weeks 25mg/kg/day (rat), 100mg/kg/day (mice) Rats and Mice 25mg/kg/day (rat), 100mg/kg/day (mice) EHC 216 (2000)

4.5.5.3 Corrosion/Irritation

Exp route Species Method Results Reference Skin Human Not specified Irritant MSDS, GESAMP-BWWG Eye Human Not specified Irritant MSDS, GESAMP-BWWG Inhalation LC 50 (mg/L/4h) Human 0.03-1.2 μ g/L Irritant MSDS, GESAMP- BWWG

4.5.5.4 Developmental and reproductive toxicity

Exp route Exp duration Exp dose Species Results Reference

Oral At days 6-15 of gestation 50, 100 and 200 mg/kg/ day Rats Evidence of foetotoxic

response. No foetal malformations observed EHC 216 (2000)

Oral 105 days Rats (male and female pairs) No detectable effect on fertility, litters/pair, live pups/litter, proportion of pups born alive, sex or body weights EHC 216 (2000)

4.5.5.5 Carcinogenicity

Effect Species Method Results Reference Carcinogenicity Rats 5 days exposure/week for 2 years No evidence observed NTP, 1989a

Mutagenicity Bacteria Not identified (Ames test) In vivo Mutagenic inconclusive

Reprotoxicity Rats 5 days exposure/week for 2 years No evidence observed NTP, 1989a

4.5.6 Dibromochloromethane

Trihalomethanes in drinking water: WHO/SDE/WSH/05.08/64.MEPC 57/2/6 ANNEX Page 46

I:\MEPC\57\2-6.doc 4.5.6.1 Acute toxicity

Exp route Value Species Reference 800 Mouse MEPC 56/2, paragraph 2.3.1.2; GESAMP- BWWG Oral LD 50 (mg/L)

1186/848 (male/female) Rat Chu et al . 1980

4.5.6.2 Repeated dose toxicity

Exp
route Exp duration Exp dose Species Method Results NOAEL Reference

Oral 90 days 0-200 mg/kg/ d Rat Solved in corn oil,

gavage Decrease in body weight at 200 mg/kg/d, elevated alanine aminotransferase, centrilobular hepatic necrosis, kidney proximals tubule cell degeneration 50 mg/kg/d MEPC 56/2, para. 2.3.1.2 ; GESAMP ñ BWWG ; Daniel et al 1990

Oral 90 days 0-250 mg/kg bw/day Rat Solved in corn oil,

gavage Depressed body weight, increased hepatic vacuolation, kidney and liver toxicity 30 mg/kg bw NTP 1985

Oral 90 days 0-250 mg/kg bw/day Mouse Solved in corn oil,

gavage Kidney and liver toxicity 125 mg/kg bw NTP 1985MEPC 57/2/6 ANNEX Page 47

I:\MEPC\57\2-6.doc 4.5.6.3 Developmental and reproductive toxicity

Exp
route Exp duration Exp dose Species Method Results NOAEL NO EL Reference

Oral 2 generati

ons 0.4 mg/L Mice At 4 mg/L decreased fertility. No dominant lethal or teratogenic effects observed. n/a n/a MEPC 56/2 para. 2.3.5.2GESAMPBWWG

Oral 35 days /generati

on 0-685 mg/kg bw (0- 4000 mg/L) Mice Ad libitum, multige neratio nal Decreased body weight, enlarged livers with gross morphological changes, decreased litter size, decreased pup viability, reduced fertility and reduced F 1 generation survival 17 mg/kg bw/day n/a Borzelleca & Carchman 1982

4.5.6.4 Carcinogenicity

Effect Species Method Results Reference Carcinogenicity Human Probable human carcinogen US EPA (Iris) MEPC 56/2, para 2.3.6.2; GESAMP- BWWG; Mutagenicity Salmonella typhimurium Ames Positive and negative results MEPC 56/2, para. 2.3.7.2; GESAMP- BWWG Genotoxicity Chinese hamster ovary cells Human lyphocytes Chromosoma l aberration

test SCE-test Positive

Positive Ishidate et al 1982

Morimoto & Koizumi 1983

4.5.7 Dichlorobromomethane

Trihalomethanes in drinking wa ter: WHO/SDE/WSH/05.08/64.

4.5.7.1 Acute toxicity

Exposure route Value Species Reference Oral LD 50 (mg/L) 916/969 (male/female) Rat Chu et al . 1980MEPC 57/2/6 ANNEX Page 48

I:\MEPC\57\2-6.doc 4.5.7.2 Repeated dose toxicity

Exp
route Exp duration Exp dose Species Method Results NOAEL Reference

Oral 90 days 0-300 mg/kg bw/ day Rat Gavage Decreased body weight, centrilobular degeneration of liver, degeneration and necrosis of kidney 75 and 150 mg/kg bw/day (bw reduction and hepatic/rena l lesions respectively) NTP 1987

Oral 90 days 0-100 (m) /0- 400 (f) Mouse (m/f) Gavage Centrilobular degeneration of liver (f), degeneration and necrosis of kidney (m) 50 mg/kg bw/day NTP 1987

4.5.7.3 Developmental and reproductive toxicity

Exp
route Exp duration Exp dose Species Method Results NOAEL Reference

Oral 15 days (d6-21 of gestation) 0-82 mg/kg bw/day Rat Ad libitum Water comsumption, body weight gain and feed consumption reduced 18.4 mg/kg bw/day (maternal) 45 mg/kg bw/day (developmental) Christian et al

. 2001

Oral 23 days (d6-29 of gestation) 0-55.3 mg/kg bw/day Rabbit Ad libitum Body weight gain and feed consumption reduced 13.4 mg/kg bw/day (maternal) 55.3 mg/kg bw/day(developmental) Christian et al

. 2001

Oral 52 weeks 22 and 39 mg/kg bw/day Rats Ad libitum Decreased mean straight line average path and curvilinear velocities of

sperm IPCS 2000MEPC 57/2/6 ANNEX Page 49

I:\MEPC\57\2-6.doc 4.5.8 2,4,6-Tribromophenol

4.5.8.1 Effects on skin and eye

Exp route Species Method Results Reference Skin (LD 50 ) Rabbit Rabbit >2000 mg/kg bw >8000 mg/kg bw IRDC 1973 IRDC 1974a Inhalation LC 50 (mg/L/4h) Rat Rat 4h 1h 50 000 mg/m 3 200 000 mg/m 3 IRDC 1974a IRDC 1973

4.5.8.2 Repeated dose toxicity

Exp
route Exp duration Exp Dose Species Method Results NOAEL Reference

Oral 48 days 100- 1000 mg/kg bw/ day Rat Gavage Salivation, suppressed bw gain, decreased food consumption, increased liver weight, increased kidney weight, increased total protein, decreased bilirubin and potassium in blood, decreased thymus weight, hepatocyte hypertrophy, decreased hepatic fatty change, renal papillary necrosis and dilatation of tubules, lymphycyte infiltration 100 mg /kg bw Tanaka et al 1999

4.5.8.3 Corrosion/irritation

Exp route Species Method Results Reference Skin Rabbit OECD TG 404 One dosage (0.5g) 24h Not irritating DSBG/BCL (1985b) Eye Rabbit OECDTG 405 One dosage (100mg) Moderately irritating DSBG/BCL (1997b)MEPC 57/2/6 ANNEX Page 50

I:\MEPC\57\2-6.doc 4.5.8.4 Developmental and reproductive toxicity

Exp
route Exp duration Exp dose Species Method Results NO AEL NOEL Reference

Oral Day 0 and day 4 100, 300 and 1000 mg/kg/ day Rat Repeated dose toxicity, reproduct ion/devel opment Reduced viability and body weight 1000 mg/kg/day mother 300 mg/kg/day

pups Tanaka et al 1999

Oral 20 days 10- 3000 mg/kg/ day Rat Decreased weight gain, increased post implantation loss, decreased fetus viability 1000 mg/kg/day mother 300 mg/kg/day

pups IRDC, 1978b

Inhala tion 21 days of gestation 0.03- 1.0 mg/m 3 Rat Whole body inhalation Pre and post implantation embryo losses, decreased fetal body weight <0.03 mg/m 3 Lyubimov et al 1998

4.5.8.5 Carcinogenicity

No long-term exposure or carcinogenicity stud ies on brominated pheno ls were identified.

4.5.8.6 Genotoxicity

Effect Species Method Dose Results Reference Genotoxicity CHL/IU cells Chromosoma l aberration test ( in vitro ) 1.6 mg/ml Positive Sasaki et al 1999

Genotoxicity Mouse, bone marrow Micronucleus test ( in vivo ) 75-300 mg/kg intraperiton eally Negative DSBG /BCL (2002)

4.5.9 Dibromoacetonitrile

Halogenated Acetonitriles in Dri nking-water: WHO/SDE/WSH/03.04/98.MEPC 57/2/6 ANNEX Page 51

I:\MEPC\57\2-6.doc 4.5.9.1 Repeated dose toxicity

Exp
route Exp duration Exp dose Species Method Results NOAEL Reference

Oral 13 weeks 0.9- 12.6 mg/kg bw/da

y Rat Drinking

water ad libitum Decreased

water consumption, decreased body weight 11.3 (females) and 12.6 (males) mg/kg bw/day NTP, 2001b and 2002 a,b

Oral 14 days 23-280 mg/kg bw Rat Gavage Decreased body weight in males, increased liver weight in females 23 mg/kg bw/day Hayes et al . 1986

4.5.9.2 Developmental and reproductive toxicity

Exp
route Exp duration Exp dose Species Method Results NOAEL Reference

Oral 14 days 2-18 mg/kg bw/day Rat Drinking water, ad libitum Decreased testes weight and testicular atrophy 12 mg/kg bw/day NTP, 2000c

14 days (gestation day 7- 21) 50mg/kg bw/day Rat Intubation Decreased maternal weight gain, decreased birth weight* 50 mg/kg bw/day** Smith et al . 1987

* Dibromoacetonitrile were solved in tricap rylin which is proven to be a development toxicant and hence possibility of potentiating de velopmental effects of trihaloacetonitriles and probably other haloacetonitriles. ** only one dose administered.

4.5.9.3 Genotoxicity

Effect Species Method Results Reference| DNA damage Escherichia coli SOS chromotest Weakly positive (without metabolic activation) Le Curieux et al . 1995

Sister chromatid exchange Chinese hamster ovary cells Exogenous metabolic activation Induction Bull et al . 1985

Human lymphoblastic cells DNA strand breaks Daniel et al 1986MEPC 57/2/6 ANNEX Page 52

I:\MEPC\57\2-6.doc 4.5.10 Monobromoacetic acid

No data on mammalian toxicology for Monobrom oacetic acid from the current databases is available.

5 HANDLING AND USE OF THE OS BWMS

5.1 General

A complete set of documentation describing the OS BWMS and particul ars of the specific installation follows each delivery. A set of such is enclosed to this application describing the system as installed on board the M/V Hˆegh Trooper. The system documentation includes arrangement drawings, data and specification sheets, operational manuals and spare part references. With all standard components such as pumps, co mpressors, the nitrogen generator, etc., the suppliersí documentation is also enclosed.

The operational manual provides information enabli ng proper use of the system and includes safety instructions and mainte nance programme. Officers and crew members involved in ballast water operations and/or the maintenance of ball ast water systems should be made familiar with all features of the OS BWMS and further should undergo training in the operation and maintenance of all such features.

In the following, the main system components are described. In addition to the focused systems, there are some supporting systems and components such as filter, valves, pumps, etc. These are not described in detail here as they are of standard design a nd well known to both crew and officers. Their usage, maintenance requirements, etc., are, however, included in the OS BWMS documentation and training package.

5.2 Circumferential cavitation ñ C3T

The cavitation unit is a static and passive component integrated into the main ballast water pipe, as illustrated in Figure 5 below. The sub-unit cavitation devices and energy release zones are constructed from a homopolymer with approximately one-third of the tensil e strength of steel. The material has a melting point at 175°C. Howeve r, all components made from this material are insulated and built-in into a pipe casing as a section of the sta ndard piping in the engine room. Thus, in the case of an engine room fire, a potential melting of the components constructed from homopolymer will not affect the inte grity of the ballast water system.

The cavitation chamber may be periodically ch ecked by installing hydrophones. OceanSaver has developed a control programme used for co mmissioning that will verify the cavitation characteristics of the system.

Cavitation is usually associated with erosion, e.g. particularly problems in propulsion as well as in pump impellers. This is a pheno mena arising as a consequence of the release of high pressure pulses as cavities (bubbles) ge nerated are exposed to a higher internal fluid pressure and implodes. The C3T unit applies this released en ergy to the flow direc tion of the water using surfaces and geometry to initiate cavitation. Th is application avoids di rect exposure to these surfaces. However, the components in the energy z one are considered as replacement parts with an expected life span of 3 years operation. The C3T delivery includes one set of replacement cassette (C3T sub-unit). Replacement should be made after 3 years or 2000 hrs operations.MEPC 57/2/6 ANNEX Page 53

I:\MEPC\57\2-6.doc The automation system will provide a reminder. Re placement is simple and can be undertaken by trained crew.

Figure 5: C3T unit incl uding 18 C3T sub-units.

5.3 The C2E unit

The C2E unit is a self contained fully automatic pressurized close-circuit modular system. It has built in redundancy which allows periodic use of individual modules and the availability of spares if a system module fails.

The C2E unit comprises four main components:

- Control/ automation and monitoring including calibration; - Power supply/ converter; - Electrodialytic cell modules;and - Ventilation loop.

These components are built into a singular cabinet that may be located independently from the actual location of the ballast wa ter line and associated component s. The cabinet configuration depends upon the planned location of the unit, e.g. for the installation in potential dangerous areas specific requirements will apply to the cabinet and all its connections.

Features include a calibration l oop which at set intervals is act ivated to calibrate operational characteristics appropriate for the water in whic h the vessel is operating in as well as automatedMEPC 57/2/6 ANNEX Page 54

I:\MEPC\57\2-6.doc cleaning by reverse charge following ballasting op erations. Options are in place allowing vessels periodically operating in fresh wate r to be fitted with the system.

The actual cell modules are automa tically cleaned by applying reve rse charge. Apart from this cleaning process, there are no required maintena nce requirements other than a system check co-ordinated with the ve ssels general maintenance programme/class procedures.

The C2E unit is built in accordance with all relevant standards and regulations and its actual specific installation is subject to class approval.

5.3.1 Training

Training in the safe operation and maintenance of the C2E equipment and its safe application on board the ship is provided upon commissioning to the ship's officers and crew. New crew members should be trained promptly. Training must include the following:

.1 safe operation of the C2E uni; and .2 awareness of system performance during operation.

There are no handling or st orage issues involved in the operatio n of this system. Hazards awareness associated with potential fume build up is es pecially important for all the officers.

5.3.2 Fire-fighting measures

There are neither special fire-fighting require ments for the solutions produced by the C2E unit nor for the processes applied for their producti on. The C2E disinfectant is regarded as not flammable.

5.3.3 Safety issues ñ Precautions

All components used in the C2E system are approved for shipboard use. Electrical components, pressure components and other sy stem components are fully comp liant with all relevant class requirements.

Installation precaution:

- Ensure that the chosen location for th e system is qualified with respect to operational conditions (temperature/ humidity/ ventilation).

- The unit may be affected by strong magnetic fields. To ensure durability, installation on vibration dampening is advised.

Ventilation

The C2E cabinet is equipped with internal ven tilation to ensure proper cooling and efficient evacuation of any gas that may be generated duri ng operations. As the system is pressurized and close-circuited, any gas produced is rapidly co mpressed and partly re-d issolved. There are no releases of any gas, fumes or vapor to the im mediate vicinity unless a malfunction occurs. When the C2E disinfectant re-enters the main ballast wa ter line, any remaining gas is further diluted and re-dissolved in the water. Safety is fu rther enhanced by gas monitoring sensors on theMEPC 57/2/6 ANNEX Page 55

I:\MEPC\57\2-6.doc exhaust side of the internal ve ntilation system monitoring potenti al accumulated chlorous gases and hydrogen. This is incorporated in the automation system. Elevat ed levels will initiate the auto-stop function of the un it. It should be noted that the systems close circuit design prevent any direct exposure of the electrodi alytic process to atmosphere; further, that no residuals are produced avoiding potential vapor-off. This reduces the potential formation of gas in the cell cabinet considerably. The powering of the unit comp ared to the flow over the cell is a further safety feature limiting any production of hydrogen to less than those creating explosive atmospheres with a safety margin of 4.

Electrical connections

All electrical components and connections incl uded in the C2E unit ar e built according to regulations for shipboard use. Connections fr om the ships supply to the C2E unit must be according to current electrical requirements a nd carried out by qualified licensed personnel. Ensure that the electrical supply is compliant wi th the requirements of th e unit. (380 Volts, each phase 16A). The unit must be earthed.

Maintenance

The C2E unit must not be opened by unauthorized personnel. All servicing should be referred to trained and qualified service personnel.

5.4 Handling and use of the Nitrogen Supersaturation Unit

5.4.1 General

The Nitrogen supersaturation unit compresses air which is fed through a membrane-based nitrogen generator to produce nitr ogen. The nitrogen is then inject ed into a portion of the ballast water taken off the main line and mixed over a static mixer. This flow is then re-injected into the main pipe and mixed again resulting in supe rsaturation. As a consequence of this, oxygen dissolved in the ballast water is released.

Both the compressor as well as the membrane based nitrogen gene rator are standard components supplied for shipboard use. The injection compone nts are passive units w ith the exception of a pump, again a standard unit designed, bu ilt and certified for shipboard use.

On-board produced nitrogen ha s an oxygen content of approxi mately 0.5% by volume. This makes the inert nitrogen gas a non-toxic but asphyxiating gas which mu st not be inhaled.

The nitrogen producing components may be installe d independently of th e ballast water pipe. However, whatever location is chosen requi res to have appropriate ventilation.

The nitrogen system is a pressurized system operat ing at 4 to 6 bar. Working pressure is set for the individual installation. Any pr essure loss in the system will initiate an alarm and system auto-stop.MEPC 57/2/6 ANNEX Page 56

I:\MEPC\57\2-6.doc 5.4.2 Precautions to be observed at all times

.1 At no time shall any person enter any space under Nitrogen gas treatment or any space with potential Nitroge n gas migration and an O xygen deficient atmosphere without breathing equipment or before it is thoroughly ventilated and checked.

.2 All access to spaces under Nitrogen gas or areas under potential Nitrogen gas migration are locked, secured and clearly marked with ìDangerousî warning signs made up in English and all applicable languages are to be exhibited at all manholes.

.3 Ballast tank manholes under Nitrogen ga s treatment must never be opened and entered without the correct pr ocedures being carried out.

.4 In an Emergency situation, the valve fo r the Nitrogen gas system is locked with a padlock. The key for the valve will be held by the following crew: Master, Chief Engineer, Chief Officer, Second Engineer.

5.4.3 Training

Training in the safe operation and maintenance of N2 equipment and its safe application aboard ship is to be given to the shipís officers an d crew. New crew members should be trained promptly. Training must include the following:

.1 recognition of posted danger placards; and

.2 awareness of the properties of Nitrogen.

Nitrogen hazard awareness is especia lly important for all the officers.

5.4.4 Handling and Storage

Safety equipment must be available when dealin g with Nitrogen gas. The minimum complement of safety equipment should include:

.1 Portable oxygen monitor ñ A Nitrogen filled space is dangerous because of the low oxygen content of the atmosphere. A Nitrogen filled compartment (ballast tank) typically contains less than 5% oxygen. It is therefore essential to have the correct instrumentation, this being, a portable oxygen monitor to assess the level of oxygen within the space before entering. It is also esse ntial that this instrument is properly calibrated. Fresh air with a standard oxygen concentration of 21% is used in calibration.

.2 Warning signs in applicable languages ñ A Nitrogen-filled space should be clearly labelled with caution and danger signs. Manholes must be bolted prior to the Nitrogen treatment being started and ke pt closed until th e Nitrogen supply has been turned off, the space gas freed, and declared safe to enter.

Storage : The nitrogen consumption is supplied on demand and thus, there are no storage requirements. However, for certain applications , Nitrogen may be suppl ied produced for storage or delivered from existing on-board Nitrogen faci lities. In any such case, all systems will beMEPC 57/2/6 ANNEX Page 57

I:\MEPC\57\2-6.doc designed and built according to re levant requirements. Any such sy stems will be subject to class approval.

It is important that the ships crews are fam iliar with the symptoms of asphyxiation whilst working with Nitrogen and the concentrations at which this can occur. The following table provides a guideline to these symptoms:

Table 5: Symptoms of asphyxiation

Oxygen % Symptom 21% Breathing, all functions normal. 19-19.5% Oxygen monitor alarm level. 17% Candle is extinguished. 12-16% Breathing rate is increased and pulse rate accelerated. Ability to maintain attention and to think cl early is diminished, but can be restored with effort. Muscular coordination for finer skilled movement is disturbed. 10-14% Consciousness continues but j udgement becomes faulty. Severe injuries, burns, bruises etc., may cause no pain. Muscular effort leads to rapid fatigue, may permanently damage the heart and cause fainting. 6-10% Nausea and vomiting may appear. Legs give way; person cannot walk, stand or crawl. This is often the first and only warning and it comes too late. The person may r ealize he is dying but does not care. No pain is felt. Less than 6% Loss of consciousness in 30-45 seconds if resting, sooner if active. Breathing in gasps followed by convulsive movements, then breathing stops. The heart may con tinue beating for a few minutes then it stops.

When an individual is exposed to a low oxygen concentration, asphyxia tion will occur quickly and without any warning sign. To an obser ver, the symptoms of oxygen deprivation are increased pulse and breathing rate. To the e xposed individual, the symptoms are fatigue, abnormal perceptions or responses, dry throat, headache and sickness.

Exposure to an atmosphere with a low concen tration of Oxygen does not necessarily produce recognizable symptoms before unconsciousness occu rs. The onset of brain damage and the risk of death can follow within a few minutes. If th e oxygen deficiency is not sufficient to cause unconsciousness, the mind is liable to become apathetic and complacent, and even if these symptoms are noticed and escape is attempted, physical exertion will aggravate the weakness of both the mind and the body.

Persons showing signs of oxygen deprivation should be moved immediately to a normal atmosphere. If the person is unc onscious, check for pulse and brea thing. Continue to monitor vital life signs. If the pulse or breathing has stopped, cardiopulmonary resuscitation (CPR) must be carried out. If both pulse and breathing are present, the person should recover without assistance.

There is a danger to shipsí crew and shore personnel of Nitroge n gas escaping or migrating into spaces adjacent to a Nitrogen-filled space. It is important to recognize that a hazard may existMEPC 57/2/6 ANNEX Page 58

I:\MEPC\57\2-6.doc and that sufficient ventilation precautions are observed prior to entering or approaching areas where Nitrogen gas may exist. Some of these spaces may be as follows:

.1 Expected Spaces ñ Ballast tanks, air vent ilation pipes from tanks; .2 Unexpected Confined Spaces ñ Cable trunks, nitroge n generating area; and .3 Known Nitrogen Migration Paths ñ Piping and electrica l cable penetrations.

After a space is ventilated thoroughly, it is necessar y to check the atmosphere at different heights and locations to ensure that no pockets of oxyge n-deficient atmosphere remain. It must be remembered that inert gas/Nitrogen is s lightly lighter than air in general.

5.4.5 Emergency measures

Measures should be integrated in the vessels general safety plan.

Emergency first aid

In the event that a rescue needs to be carried out from an area under Nitrogen gas treatment the following procedure will be adopted:

.1 raise the alarm by informing th e bridge or duty deck officer; .2 close all CA control valves to the appropriate CA zones; .3 open all inlet and outlet ve nts on the fresh air system to the appropriate zones; .4 commence maximum fresh air ventilation; .5 assemble emergency/recovery team and equipment; .6 when normal atmosphere has been ac hieved rescue becomes possible; and .7 when rescue is made, continue to mon itor vital life signs and carry out appropriate first aid and recovery procedures.

Fire-fighting measures

Nitrogen is a true inert gas a nd is non-explosive. It does no t represent a fire hazard.

Accidental release

In the event of Accident al release, the following procedure will be adopted:

.1 maximum fresh air ventilat ion must be carried out to make that zone and passages to the zone free from Nitrogen;

.2 entry into confined spaces may only be carried out after completion of ìPre entry proceduresî by the Shipís Safety Officer;

.3 after the Nitrogen generator has been shut down, the supply valves locked and the Nitrogen spaces ventilated, each of the ad jacent spaces must be ventilated; and

.4 when all ventilating has been acco mplished for the entire ship, the N 2 warning signs should be removed or covered.MEPC 57/2/6 ANNEX Page 59

I:\MEPC\57\2-6.doc 6 RISK CHARACTERIZATION

6.1 Screening for persistency, bioaccumulation and toxicity

Criteria for evaluating the long-term persisten ce, bioaccumulation and t oxicity, the so-called PBT criteria have been decided by several organi sations and in several protocols and policies. The EU PBT criteria have decided the followi ng criteria for persiste nce, bioaccumulation and toxicity (Table 6).

Table 6: Criteria for identi fication of PBT substances

Criterion PBT Criteria P Half-life > 60 d in marine water or > 40 d in freshwater or half-life > 180 d in marine sediment or > 120 d in freshwater sediment B BCF > 2,000 T Chronic NOEC < 0.01 mg/L or CMR or endocrine disrupting effects

6.1.1 The P criterion

None of the Active Substances or the Relevant Chemicals has a half-life exceeding 60 days in marine water. Subsequently, there is no Active Substance or Relevant Chemical within the OS BWMS that fulfils the P criterion for being persistent.

6.1.2 The B criterion

The B criterion can be decided by ca lculating the BCF (bioconcentration factor, weight basis) for each substance. If BCF values are not at hand, as here is the case, the relation between BCF and the octanol/water partition coe fficient can be described as:

70

. 0 log 85

. 0 log

− ⋅ = Kow BCF ( Ref. TGD part II p. 126 )

Therefore, a log K ow value has been calculated for each substance to give a corresponding BCF presented in Section 4. Nevertheless, most substances produced in the electrolysis of the OS BWMS are in ionic form, and ions are in general considered to accumulate to insignificant extents. The log K ow hereby presented, and the corresponding BCF values can confirm that observation. Octanol/Water pa rtition coefficient, logP are derived from http://www.molinspiration.com/cgi-bin/properties

.

It can be concluded that none of the chosen Active Substances or Relevant Chemicals can be addressed as being bio accumulative.

6.1.3 The T criterion

To fit the T criterion the NOEC value of the substance shall be < 0.01 mg/L. According to the ECOTOX database search presented in Section 4, only chlorine fits th at criterion with an LC 50 for the Acartia tonsa of 5 μ g/L.MEPC 57/2/6 ANNEX Page 60

I:\MEPC\57\2-6.doc 6.2 PEC ñ PNEC assessment

6.2.1 PNEC estimation

If sufficient toxicity data is at hand, a PNEC (P redicted No Effect Concentration) value for an Active Substance or Relevant Chemical can be derived, by using the systematic approach described in the Technical Guidance Document on Risk Assessment by the European Chemicals Bureau, part II (TGD). The PNEC value is the best indicativ e for evaluating the toxic behaviour of the Active Substances and Relevant Chemicals.

A PNEC value can be estimated by using the assessment factors proposed in the Technical Guidance Document on Risk Assessment by the European Chemicals Bureau, part II (TGD II). The notes (a), (b), (c) and (d ) can be found on page 149 in the Technical Guidance Document on Risk Assessment by the European Chemicals Bureau, part II.

There is no sufficient data available for estima ting PNEC values for all above presented Active Substances and Relevant Chemicals. Derive d PNEC values are given in Table 7.MEPC 57/2/6 ANNEX Page 61

I:\MEPC\57\2-6.doc Table 7: Estimated PNEC values for Acti ve Substances and Relevant Chemicals

Toxic substance Available data Assessment factor PNEC

Hypochlorous acid Two long-term NOECs from freshwater or salt-water species representing two trophic levels 500 0.096 μ g/L

Bromoacetic acid Two long-term NOECs from freshwater or salt water species representing two trophic levels 500 0.12 μ g/L

Tribromomethane One short-term EC 50 from each of three trophic levels of the base set (fish, Daphnia and algae), but where at least the acute toxicity for Daphnia is determined. 10 000 0.29 μ g/L

2-Bromophenol One long-term NOEC from freshwater or salt water crustacean reproduction 1000 0.22 μ g/L

Chlorine dioxide LC 50 values from two freshwater fish species, marine crustacean and marine algae 10 000 0.25 μ g/L

Ozone LC 50 values from 6 freshwater fish 10 000 0.93ng/L

Bromoform LC 50 from two freshwater fish, one freshwater and one ma rine crustacean and one freshwater algae 1000 0.29 μ g/L

Dibromochlorome thane LC 50 from one fish species 10 000 5.2 μ g/L

2,4,6 Tribromophenol LC 50 from one fish species (3 studies), one crustacean and one algae. Chronic effects from one algae 1000 0.5 μ g/L

Dibromoacetonitrile LC 50 from one fish species, chronic effects from two algae 10 000 0.055 μ g/L

Monobromoacetic acid LC 50 from 2 fish species and one crustacean. Chronic effects on one crustacean and one algae 1000 1.6 μ g/L

The lowest PNEC value is derived for Ozone wi th a PNEC of 0.93 ng/L. However, Ozone has a half-life around 5.3 seconds in se awater and is produced in low c oncentrations of the C2E unit. Ozone is, therefore, not relevant in a PEC ñ PN EC assessment for ballast water discharged at least 24 hours after treatment. Taking into account the half-life and other data presented in section 4, the most Relevant Chemical com pound seems to be hypochlorous acid, with a PNEC value of 0.096 μ g/L.

6.2.2 PEC values in discharged ballast water

Predicted environmental concentration (PEC) of Active Substances and Relevant Chemicals in discharged ballast water from ships can be estima ted from direct measurements of chemicals in treated seawater or estimated indirectly by measuring the oxidant level in the treated water.MEPC 57/2/6 ANNEX Page 62

I:\MEPC\57\2-6.doc 6.2.2.1 Residual oxidant level

Remaining concentrations of fr ee and total residual oxidants in the treated ballast water at discharge was measured with standard colo rimetric methods (HACH-Lange: DPD method; SM 4500-Cl G, USEPA 330.5). Free residual oxidant (see Textbox 2) measured with this method includes hypochlorous acid, hypoc hlorite ions, hypobromous acid and hypobromite ion,and total residual oxidant includes also the halogenamines and other less eff ective oxidants with N-C link.

Oxidant decay was monitored following treatment of seawater with wate r qualities corresponding to the requirements in the Guidelines (G8) (int ermediate salinity) (Table 10, Figures 6 and 7). Three tests were carried out on 9 May 2007 with va rying dosages of anolyte. Tests Nos. 2 and 3 correspond to the dosage that is us ed in the full scale version.

Table 8: Measured water qualities in treated seawater in small scale tests (35 m 3 /hr) from 9 May 2007.

TSS mg/l DOC, mg/l POC, mg/l Test on 9 May Average Stdev Average Stdev Average Stdev Required level (G8) > 50 - > 5 - > 5 -

Control water 58.10 0.36 8.17 0.06 10.57 0.15 Treated water 64.37 0.4 9.10 0.0 11.23 0.35

Test 9 May 2007 Salinity: 23.7 psu, Temp: 12C

0 0,5

1 1,5

2 2,5

0:00:00 12:00:00 24:00:00 36:00:00 48:00:00 60:00:00

Time (hours)Total chlorine mg/L Test 1

Test 2

Test 3

Figure 6: Total oxidant decay after treatmen t of surface seawater with three levels of anolyte (test 1: 3 L/m 3 , 2: 6 L/m 3 , 3: 9 L/m 3 ).MEPC 57/2/6 ANNEX Page 63

I:\MEPC\57\2-6.doc Test 9 May 2007 Salinity: 23.7 psu, Temp: 12C

0 0,5

1 1,5

2 2,5

0:00:00 12:00:00 24:00:00 36:00:00 48:00:00 60:00:00

Time (hours)Free chlorine mg/L Test 1

Test 2

Test 3

Figure 7: Free oxidant decay after treatmen t of surface seawater with three levels of anolyte (test 1: 3 L/m 3 , 2: 6 L/m 3 , 3: 9 L/m 3 ).

Probably due to high content of organic matter, the concentration of bot h TRO and Free oxidant is not detectable after less than 24 hours.

Results from similar tests carried out on 23 May 2007 are presented in Figure 8 and 9 with corresponding water quality data in Table 10. Tests T-4 and T-9 ar e with seawater spiked with organic matter and particles. Test N-1 is with na tural seawater from the surface layer of the Oslo fjord with no addition of particles or organic ma tter. The normal concentrations of organic matter in the surface layer of the Oslo fjord correspond to relative clean harbour water. Salinity during test was 21.5 psu and temperature in influent water was 11.8oC.

Table 9: Measured water qualities in treated seawater in small scale tests (35 m 3 /hr) 23 May 2007.

TSS mg/l DOC, mg/l POC, mg/l Test on 23 May Average Stdev Average Stdev Average Stdev Test T-4 and T-9 62.93 0.93 9.17 0.06 8.90 1.76 Test N-1 4.87 0.90 2.13 0.06 0.23 0.06

Test 23 May 2007 Salinity: 21.5 psu Temp: 11.8 C

0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0

0:00:00 2:24:00 4:48:00 7:12:00 9:36:00 12:00:00 14:24:00 16:48:00 19:12:00 21:36:00 24:00:00

Time (hours)Total available oxidant (mg Cl/L)

N-1

T-4

T-9

Figure 8: Total oxidant decay after treatm ent of surface seawater with varying water quality (also see Table 10).MEPC 57/2/6 ANNEX Page 64

I:\MEPC\57\2-6.doc Test 23 May 2007 Salinity: 21.5 psu Temp: 11.8 C

0,0 0,5 1,0 1,5 2,0 2,5 3,0

0:00:00 2:24:00 4:48:00 7:12:00 9:36:00 12:00:00 14:24:00 16:48:00 19:12:00 21:36:00 24:00:00

Time (hours)Free oxidant (mg Cl/L) N-1

T-4

T-9

Figure 9: Free oxidant decay after oxidant treatment of surface seawater with varying water quality (also see Table 10).

The results for T-4 and T-9 with ìG8-water qual ityî follow the results from 9 May with rapid decay in less than 6 hours. In ìunpollutedî water (Test N-1) oxidants are detectable at low levels more than 24 hours.

6.2.2.2 Measured concentration of chemical components

In June 2007 a >200 m 3 /h version of the OceanSaver Balla st Water Management System (OS BWMS) was installed and operated at the Solbergstrand test facility. A tank with more than 500 m 3 of challenge water was prepared in accordance w ith the Guidelines (G8) for 2-32 psu water. More than 200 m 3 of the challenge water was treated in a ballasting operation of the OS BWMS (treated water), whilst >200 m 3 of the challenge water was pumped, using the same pump system, through a bypass of the BWMS (cont rol water). More than 200 m 3 of each of treated water and control water was collected in separate tanks and samples were taken from each for analysis of certain oxidation by-products (Day 0: 20.06.2007). After 5 days of storage, >200 m 3 of the Treated water was treated in a deballasting operation whilst >200 m 3 of the Control water was pumped, using the same pump system as th e OS BWMS, through a bypass of the system (deballasted Control wa ter). More than 200 m 3 of each of deballasted Treated water and deballasted Control water was co llected in separate tanks and samples were removed from each for analysis of certain oxidat ion by-products (Day 5: 25.06.2007). The results from the analysis can be found in Table 10.

The results are likely to be highly dependent on the operational settings of the C2E unit in the OS BWMS and the ambient features of the treated balla st water. In the initia l test in June 2007 the concentration of Active Substances was slightly higher (> 3 mg/L measured as Free chlorine) than it will be in normal operation (approx. 2 mg/L). More analyses have been and will be carried out of treated water in the land-based tests at Solbergstrand from August to October 2007.MEPC 57/2/6 ANNEX Page 65

I:\MEPC\57\2-6.doc Table 10: Analysis results of oxidation by -products from samples collected during an initial test of OS BWMS at Solbergstrand, June 2007 (NIVA 2007b).

Chemical Name Control day 0 Control day 5 Test day 0 Test day 5

μ g/l μ g/l μ g/l μ g/l AOX 29 <500 386 1290 EOX < 50 < 50 < 50 < 50 2-monochlorophenol <0.100 <0.100 <0.100 <0.100 3- monochlorophenol <0.100 <0.100 <0.100 <0.100 4- monochlorophenol <0.100 <0.100 <0.100 <0.100 2,3-dichlorophenol <0.100 <0.100 <0.100 <0.100 2,4+2,5-dichlorophenol <0.200 <0.200 <0.200 <0.200 2,6-dichlorophenol <0.100 <0.100 <0.100 <0.100 3,4-dichlorophenol <0.100 <0.100 <0.100 <0.100 3,5-dichlorophenol <0.100 <0.100 <0.100 <0.100 2,3,4-trichlorophenol <0.100 <0.100 <0.100 <0.100 2,3,5-trichlorophenol <0.100 <0.100 <0.100 <0.100 2,3,6-trichlorophenol <0.100 <0.100 <0.100 <0.100 2,4,5-trichlorophenol <0.100 <0.100 <0.100 <0.100 2,4,6-trichlorophenol <0.100 <0.100 <0.100 <0.100 3,4,5-trichlorophenol <0.100 <0.100 <0.100 <0.100 2,3,4,5-tetrachlorophenol <0.100 <0.100 <0.100 <0.100 2,3,4,6-tetrachlorophenol <0.100 <0.100 <0.100 <0.100 2,3,5,6-tetrachlorophenol <0.100 <0.100 <0.100 <0.100 pentachlorophenol <0.100 <0.100 <0.100 <0.100 trichloromethane/chloroform <0.300 <0.300 <0.300 <0.300 tribromomethane/bromoform <0.200 0.822 385 398 Dibromochloromethane <0.100 <0.100 14.7 17.8 Dichlorobromomethane <0.100 <0.100 0.297 0.337 CCL4-V <0.05 <0.05 <0.05 <0.05 CHBR3-V 0.03 0.29 s170 s170 CHCL3-V <0.05 <0.05 <0.05 <0.05 DBRCM-V <0.02 0.02 4.2 4.5 DCBRM-V <0.05 <0.05 0.13 0.11 TCE-V <0.3 <0.3 <0.3 <0.3 TECE-V <0.05 <0.05 <0.05 <0.05 TRCE-V <0.05 <0.05 1.5 1.4

6.2.3 PEC ñ PNEC estimation

The preliminary results based on ava ilable data from pre-tests with higher oxidant levels than in normal operation indicate that seve ral of the chemicals in Table 6 may have a PEC: PNEC ratio larger than 1 in discharged treated ballast water. With a dilution factor around 100, the discharged ballast water will have PEC: PNEC below 1.MEPC 57/2/6 ANNEX Page 66

I:\MEPC\57\2-6.doc 6.3 Ecotox testing of treated ballast water

A full ecotox evaluation will be reported in the Final Approval application. Currently, limited information is available from these tests.

6.3.1 Ecotox testing of similar systems

A toxicological study of the Active Substances and Relevant Chemi cals produced in an electrolytic process comparable to the C2E uni t in the OS BWMS has been performed by the Institute of Chemistry at Tallinn Technical University (Munter et al. 1999), for checking the presence of toxic disinfection by-products and to measure the acu te toxicity of the anolyte. Toxicity tests with both me dium (Free active chlorine ~350 mg/L) and strong (Free active chlorine ~500 mg/L) anolyte were used for 24-h acute toxicity tests of Daphnia magna according to Finnish Standard SFS 5062

. No acute effects were found for the anolyte diluted 1:500 or more and no significant differences between the two anolyte qualities were observed.

Another study performed by the same scientific t eam, investigated the chronic toxicity of the same anolyte, by performi ng a 21-day full-life cycle Daphnia magna test (Munter et al ., 2000). Mortality and reproduction were measured. The chronic test was performed with medium (C ac ~350 mg/L) and strong (C ac ~500 mg/L) anolyte at the de termined maximum effective concentrations of 1:500 and 1:1000, respectivel y. The study concluded that no chronic toxic effects could be observed.

These two toxicological studies can not be said to be perfectly corre sponding to the toxicity of the anolyte of the OS BWMS, as the anolyte in the two studies have been produced from brine and not from seawater. However, the result of the t oxicological studies can be used for giving the main frame for the toxicity of the OS BWMS. Both studies indicate low or no toxicity if Active Substance is diluted to concentrations around 1 mg/L (Free chlorine) in treated water.

The concentration of total residual oxidant in th e anolyte produced in the C2E unit of OS BWMS is between 800 and 1000 mg/L. The theoretical calculated dosage of Active Substance measured as total residual oxidant in the OS BWMS is approximately 4-5 mg/L. Due to initial oxidant decay measured concentrations of total and free residual oxidant are around 1.5 and 2.5 in treated ballast water. After 24 hours, the concentration in polluted seawater is not detectable. In unpolluted coastal water, oxidants may be detectable 48 hours after treatment.

6.3.2 Initial ecotox testing of ballast water treated with OS BWMS

Four ecotox test reports from NIVA of treated balla st water are available from the pre-test of the OS BWMS 20 June 2007 and one test report from th e ordinary full-scale land-based G8 tests. Samples taken immediately after treatment with th e C2E unit (Day 0 tests) have both acute and chronic toxicity. Samples from discharged ballast water (Day 5 test) have either low or no acute toxicity and must be diluted 1:1 for no chronic toxicity.

Full toxicity assessment will be pr ovided for the Final Approval.MEPC 57/2/6 ANNEX Page 67

I:\MEPC\57\2-6.doc 7 RISK ASSESSMENT

7.1 Risk to safety of ship

Ships ballast water systems and, in particular, ballast water tanks are in many ways critical to the integrity of the ship simply because failure may cause flooding.

Additional technologies and componen ts installed on board ships may pose a threat to the general safety due to:

- the characteristics of the actual technology installed; and - potential diversion of focus as officer s and crew, already heavily loaded with various work-tasks, have to spend time on additional systems.

The OS BWMS is developed in close encounter with the shipping indus try by well experienced institutions well aware of the cons traints, risks, but also the possibilities, as relevant in this context to the shipping industry. Safety has been the main priority in this work. Consequently, the product includes only well es tablished and recognized com ponents known from shipboard use wherever possible. All components and systems particular to the OS BWMS have been developed with safety in mind and in acco rdance with all releva nt requirements.

The system is fully automatic. Ballast operation s will be carried out conventionally by the crew, thus not requiring level settings or other pre- actions. Further, maintenance requirements are integrated with the periodic survey programmes as required and with the vessels overall maintenance system.

7.1.1 Ballast water tanks

The structural integrity of a vessel is susceptible to corrosion and is widely recognized, e.g. the new IMO CPS (Coating Performance Standard), wh ich requires particular corrosion protection in ballast water tanks.

By treating ballast wate r prior to entering ballast tanks, th e conventional corrosivity and/ or effects on any corrosion preventive systems will be affected in some way. OceanSaver has carried out extensive research and tests associat ed to the potential impacts its treatment may have. The OS BWMS creates a deficiency in ava ilable oxygen in the water when stored in the tanks and, consequently, oxidation of steel or coa tings is reduced. The effects of this have been verified both by full-scale studies as well as by laboratory studies.

The addition of the C2E disinfect ion introduces oxidants to the water in the tanks for a period of time. Because of the characteri stics of the process, (short half -life and low concentration in a hypoxic environment), it does not incur on the pos itive effects the reduced level of oxygen has, as it is used in low concentrations.

Results from independent full-scale testing s uggest that the OS BWMS largely eliminates potential creep corrosion in ballast tanks. These a ssessments also conclude that the OS BWMS is fully compliant with the IMO CPS.MEPC 57/2/6 ANNEX Page 68

I:\MEPC\57\2-6.doc 7.1.2 Ballast water pipe systems

All piping that is part icular for the OS BWMS is designe d as a ìby-passî of a conventional ballast water system. This prov ides the vessel with redundancy and represents an additional safety feature. It should be noted that the OS BWMS monitoring system will log and report any by-pass operations. The OS BWMSís internal pipi ng (between OS components) may either be made from conventional steel pipi ng or from elastomeric-material s. The latter is a particular development of OceanSaver based on the use or armoured rubber tubing. This product has undergone severe testing and is approved for the us e in all relevant dangerous areas (ex-areas). The elastomeric-material is particularly appropriate for retro-fittings.

7.2 Risk to human health

The Active Substances and Relevant Chemicals produced in the OS BWMS not only pose an ecotoxic effect, they can also be toxic to humans.

7.2.1 General

The liquid solution produced by the C2E unit is non-toxic in nature but contains chemical formulations that can be mildly irrita ting to eyes, skin and digestive tract.

In many electrochemical processes involving saline water, hydrogen gas may be formed. In the case of this particular application (electrodialysis ), the actual electroche mical process takes place in a pressurized closed circuit. Any gas generated is compressed a nd partly re-dissolved into the flow. When the solution is re-injected into the main flow, this process is further enhanced by dilution. There is no release of any produced gas from the process to the atmosphere (vicinity) of the unit. The unit is, however, ventilated both as a safety precaution in case of leakage but also due to cooling purposes. Integrated gas detectors will detect any gas leakage. In the case of gas detection or pressure loss in the pressurized sy stem, the electrical supply will be disconnected automatically and, thus, the system will shut down.

The system is further protected by limiting the elec trical supply to the elec trodialytic cell as a function of its flow capacity making it impo ssible to build up explosive atmospheres (concentrations above 4% Hydrogen). Note also that the tanks when filled are also inerted due to the nitrogen supersaturation feature.

As the C2E system produces the C2E disinfectan t on demand in a pressurized enclosed circuit, there are no handling or storage issu es. There are safety measures bu ilt into the system in case of failure causing leakage and thus the potential expos ure to humans. In case of leakage, the system will automatically shut down.

7.2.2 Precautions to be observed at all times

.1 Working Area: The area where the solution is being produced (the C2E unit) is required to be properly vent ilated. The unit itself has an enclosed ventilation loop. The space in which the unit is installed s hould preferably have mechanical exhaust ventilation. During the produc tion of activated solutions the exhaust ai r is warm and, therefore, a proper location should be provided. The temperature rise of the power supply is approximately 60 o C above ambient air. Ve nting to a large and well-ventilated place is desirable. Ov erheating will cause system auto-stop function to be activated.MEPC 57/2/6 ANNEX Page 69

I:\MEPC\57\2-6.doc .2 Engineering control procedures: Documented process and safety controls should be followed.

.3 Dangerous voltage: Refer internal servicing of the C2E unit to qualified service personnel. To prevent electric shock or fi re hazard, remove th e power cords from the AC supply prior to connecting or disconnecting any signal lead, prior to replacing fuse, and prior to al tering the set-up of the unit.

.4 The C2E unit must be earthed: Earthed equipment is required for safety by regulations. In no event shall the manuf acturer be liable for consequential or special damages to persons and/or objects due to failure to observe this safety rule.

7.2.3 Hazards identification

The C2E solution is classified as non-dangerous (88/279/EWG) but may cause irritation to the eyes, sensitive skin and throat:

.1 Health effects ñ skin: Exposure may cause irritation to sensitive skin or open wounds;

.2 Health effects ñ eyes : The solution may cause irritation to the eyes; and

.3 Health effects ñ ingestion : Swallowing of the solution may cause irritation to the throat and digestive tract.

Conventional personal protective equi pment (PPE) is considered adequate in order to protect against accidental exposure (i.e. gloves, and goggles).

In case of ventilation breakdown or leakage, there is a risk of vapour or fumes to be released. These fumes may cause dizziness and nausea and inhalation should be avoided.

The C2E solution does not react with other materials, therefore, it is stable and may be stored in sealed plastic containers.

Where the C2E unit is operated, the fo llowing equipment should be available:

.1 Hand protection : Protective gloves s hould be available; .2 Eye and facial protection : No requirements; .3 Inhalation: Respiratory protection s hould be available; and .4 Body protection : Normal industrial work wear should be available.

7.2.4 Emergency measures

In the case of an emergency, the system will s hut down and the electrical supply is disconnected. The production of the C2E disinfect ant will stop immediately.

In the case of leakage, the quantity to enter the space is limited to the quantity in the actual cell. The liquid does not pose a fire ha zard as it is not flammable. It is further biodegradable. The space contaminated by the liquid may be cleaned by conventional means.MEPC 57/2/6 ANNEX Page 70

I:\MEPC\57\2-6.doc 7.2.5 Emergency first aid

In the case of first aid emergency, the following procedures should be followed:

.1 Eye contact : Where irritation occurs, fl ush with cool fresh water;

.2 Skin Contact : Where irritation occurs, wash the skin with soap and warm water;

.3 Ingestion : Drink cool fresh water to flush through and dilute; and

.4 Inhalation : Move to fresh air. If dizziness and nausea persist seek medical attention.

7.3 Risk to the aquatic environment

A study carried out by DNV (2007) i nvestigated the dilutio n of six typical s cenarios of ballast water discharge in a harbour recipient. A total ballast water volume of 50,000 m 3 is assumed discharged at a rate of 6,000 m 3 /h. A typical harbour dept h of 20 m is assumed.

The discharge velocity is assumed to be just le ss than 4 m/s. A discharge pipe diameter of 750 gives a velocity of 3.77 m/s. The discharge of water is assumed to occur at 8 m depth. This may be assumed to be a ìworst case scenarioî comp ared to a surface discharge, in that a surface discharge may experience more turbulent mixing.

The initial mixing of the discharge in the recipient is modelle d using Visual Plumes. This is an industry-standard tool pr ovided by the US EPA, see www.epa.gov/ceampubl/swater/vplume/

.
A range of 6 scenarios are defined, combining 2 cases of longshore curre nts with 3 cases of density difference between discharge and recipien t, thereby investigating the effect of density and currents on the extent of the plume:

.1 no density difference, no current .2 no density difference, transverse current .3 brackish recipient, no current .4 brackish recipient, transverse current .5 brackish ballast, no current .6 brackish ballast, transverse current

A near-zone of 300 m along the qua y and 200 m from the ship side is defined. The total volume of this zone is 1,200,000 m 3 . Therefore, excluding the effect of initial momentum and longshore currents, the discharge will be diluted >20 times within this zone.

The boundary defining the near-zone has a flux area of 14,000 m 2 . The flux of discharged ballast water through this boundary, again excluding th e effect of initial momentum and longshore currents, is 0.42 m/h. Therefore, excluding the effect of initial momentum and longshore currents, it can be said that the discharge w ill be diluted >20 times within the 300 x 200 m near-zone to the discharge point, and that the flux of ballast wate r out of this zone is low.

The initial mixing of ballast water gives a diluti on of more than 20 x within 50 m of discharge. This is supported by general c onsiderations of volumes and di scharge rates, which find thatMEPC 57/2/6 ANNEX Page 71

I:\MEPC\57\2-6.doc excluding the mixing effects of the initial mome ntum, and any longshore currents, a 20 x dilution is achieved in a 300 x 200 m near zone. The harbour current pattern will aff ect the influence zone to a great extent. Tidal currents and river flows can in many cases be expected to stretch the influence zone downstream and upstream.

With these calculated initial dilutions available data indicate no significant environmental risk from discharged ballast water treated with the OS BWMS.

More detailed simulations of yearly discharges to model ports will be provided for the Final Approval.

8 REFERENCES

Anon., 1999. Report on the test of the Anolyt e produced by the unit Envirolyte, Trapido, Veressinina, Ahelik, Institute of Chemistry at Tallinn Technical University, Department of Environmental Chemistry and Technology, 1999.

Anon., 2006. Cover story. New technology combats deadly microbes. The Clinical Services Journal, 5 (4), p. 7, July 2006.

Applegate, VC., Howell JH, Hall Jr. AE., Smith M. A., 1957. Toxicity of 4,346 Chemichals to Larval Lampreys and Fishes. Spec.Sci.Rep.Fish .No.207, Fish Wildl.Serv. U.S.D.I.Washington, D.C.:157 p.

Atkinson, L.P., 1973. Effect of air bubble solution on the air-sea gas exchange. J. Geophysical Research, 78 (6): 962-968.

Behrends, B., 2006. The use of hydrodynamic cavitation for ballast water treatment in light of the provisions under Regulation D-3. paragraph 2 of the Ballast Water Management Convention (IMO, 2004). Theoretical study for MetaFIL AS.

Behrends, B., A. Wick and T. Harder, 2007. ìPre-assessment of the impact of hydrodynamic cavitation on the chemical and biological properties of ballast waterî. Institute for Chemistry and Biology of the Marine Environment (ICBM) at th e Carl von Ossietzky Univ ersity in Oldenburg, Germany. 15.01.2007.

Betzer, N., Kott, Y., 1969. Effect of Halogens on Algae-II. Cladopho ra sp. Water Res. 3(4):257-264.

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