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

I:\MEPC\59\2-11.doc

INTERNATIONAL MARITIME ORGANIZATION

IMO 

# E

MARINE ENVIRONMENT PROTECTION COMMITTEE 59th session Agenda item 2 MEPC 59/2/11 19 December 2008 Original: ENGLISH

HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Basic Approval of the Siemens SiCURE ô Ballast Water Management System

Submitted by Germany

SUMMARY

Executive summary: This document contains the non-conf idential information related to the application for Basic Approval of the Siemens SiCURE ô Ballast Water Management System under the ìProcedure for approval of ballast water management systems that make use of Active Substances (G9)î adopted by resolution MEPC.169(57)

Strategic direction: 7.1

High-level action: 7.1.2

Planned output: 7.1.2.4

Action to be taken: Paragraph 5

Related documents: BWM/CONF/36, MEPC 57/21, BWM.2/Circ.13 and BWM.2/Circ.15

Introduction

1 Regulation D-3.2 of the International Conve ntion for the Control and Management of Shipsí Ballast Water and Sediments stipulates th at ballast water management systems that make use of Active Substances to comply with the Convention shall be appr oved by the Organization.

2 The ìProcedure for approval of ballast wate r management systems that make use of Active Substances (G9)î stipulat es the required information (MEP C 57/21, annex 1, paragraph 4.2.1) and provisions for risk characterisation and analysis (MEPC 57/21, a nnex 1, section 5). According to section 6 of the Procedure (G9), the Organization should evaluate the information provided in the application.

3 The receiving competent authority in Germ any has verified the application dossier and believes it satisfies the data requirement s of the Procedure (G9) adopted by resolution MEPC.169(57).MEPC 59/2/11 - 2 -

I:\MEPC\59\2-11.doc 4 In accordance with BWM.2/Circ.13 and BWM.2/Circ.15 Germany therefore submits the non-confidential part of the manufacturerís app lication dossier in the annex. The complete dossier will be made availabl e to the experts of the GESAMP -BWWG with the understanding of confidential treatment.

Action requested of the Committee

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

***MEPC 59/2/11

I:\MEPC\59\2-11.doc ANNEX

NON-CONFIDENTIAL INFORMATION ON THE SiCUREô BALLAST WATER MANAGEMENT SYSTEM (GERMANY)

Table of contents

List of abbreviations Index of tables Index of figures

1 INTRODUCTION

2 DESCRIPTION OF THE SIEM ENSí SiCUREô BWM SYSTEM

2.1 Basics of chlorine disinfection re levant to ballast water treatment 2.2 Control of disinfection 2.3 SiCUREô BWMS configuration

3 IDENTIFICATION OF THE PREPARATION, ACTIVE SUBSTANCE, BY-PRODUCTS AND RELEVANT CHEMICALS (G9: 4.1)

3.1 Active Substances 3.2 Relevant Chemicals

4 DATA-SET FOR ACTIVE SUBSTANCES AND PREPARATIONS (G9: 4.2)

4.1 Data sets on effects on aquatic plan ts, invertebrates and fish (G9: 4.2.1.1) 4.1.1 Acute aquatic toxicity 4.1.2 Chronic aquatic toxicity 4.1.3 Endocrine disruption 4.1.4 Sediment toxicity 4.1.5 Bioavailability/biomagnification/bioconcentration 4.1.6 Food web/population effects 4.2 Data on mammalian toxicity (G9: 4.2.1.2) 4.2.1 Acute mammalian toxicity 4.2.2 Skin, eye and sensitization effects 4.2.3 Repeated-dose toxicity 4.2.4 Chronic mammalian toxicity 4.2.5 Developmental and reproductive toxicity 4.2.6 Carcinogenicity 4.2.7 Mutagenicity and genotoxicity 4.2.8 Toxicokinetics 4.3 Data on environmental fate and eff ect under aerobic and anaerobic conditions (G9: 4.2.1.3) 4.3.1 Modes of degradation (biotic and abiotic) 4.3.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient 4.3.3 Persistence and identification of the ma in metabolites in the relevant media 4.3.4 Reaction with organic matter 4.3.5 Potential physical effects on wildlife and benthic habitatsMEPC 59/2/11 ANNEX Page 2

I:\MEPC\59\2-11.doc 4.3.6 Potential residues in seafood 4.3.7 Any known inter active effects 4.4 Physical and chemical prope rties of the Active Substances, Relevant Chemicals and treated ballast water (G9: 4.2.1.4) 4.5 Analytical methods at environm entally relevant concentrations

5 USE OF THE ACTIVE SUBSTANCE (G9: 4.2.6)

5.1 Manner of application and dosage 5.2 Operational overview and process description 5.3 Retention time 5.4 System monitoring and c ontrol, crew interaction 5.5 System requirements 5.6 System reliability 5.7 System locations, considerations and limitations 5.8 Operational safety features and alarms 5.9 Various procedures and management measures 5.9.1 Fire 5.9.2 Flooding 5.9.3 Accidental release measures 5.9.4 Marine environment release 5.9.5 Conditions for control discharge 5.10 Evaluation of management measures

6 HAZARD CLASSIFICATION AND MA TERIAL SAFETY DATA SHEETS (G9: 4.2.7)

7 RISK CHARACTERIZATION

7.1 Screening for persistence, bio accumulation, and toxicity (G9: 5.1) 7.1.1 Persistence (G9: 5.1.1.1) 7.1.2 Bioaccumulation (G9: 5.1.1.2) 7.1.3 Toxicity tests (G9: 5.1.1.3) 7.1.4 PBT criteria for Active Substance (G9: Table 1) 7.2 Evaluation of the treate d ballast water (G9: 5.2) 7.2.1 Environmental data from the proof-of-concept tests 7.2.2 Determination of holding time (G9: 5.2.7) 7.3 Risk characterization and analysis (G9: 5.3) 7.3.1 Reaction with organic matter (G9: 4.2.1.3) 7.3.2 Characterization of degrada tion route and rate (G9: 5.3.5) 7.3.3 Prediction of discharge and envir onmental concentrations (G9: 5.3.8) 7.3.4 Assessment of potential for bioaccumulation (G9: 5.3.7) 7.3.5 Effects assessment 7.3.6 Effects on aquatic organisms 7.3.7 Effects on sediment 7.3.8 Comparison of effect assessm ent with discharge toxicity 7.4 Risk to the aquatic environmentMEPC 59/2/11 ANNEX

Page 3

I:\MEPC\59\2-11.doc 8 RISK ASSESSMENT

8.1 Risk to safety of ship 8.1.1 Flooding 8.1.2 Corrosion 8.1.3 Fire/explosion 8.1.4 Accidental chemical release 8.2 Risk to human health 8.2.1 Identification of chemicals of potential concern and sources 8.2.2 Exposure assessment 8.2.3 Potential exposure health risks 8.2.4 Risk characterization 8.3 Risks to the aquatic environment

9 ASSESSMENT REPORT

9.1 Overview of data and endpoints 9.2 Test report data quality

REFERENCESMEPC 59/2/11 ANNEX Page 4

I:\MEPC\59\2-11.doc List of Abbreviations

Abbreviation Description °C Degrees Celsius AC Alternating current ACR Acute-to-chronic ratio AIS Aquatic Invasive Species BASEEFA British Approvals Service for Electrical Equipment for Flammable Atmospheres BCF Bioaccumulation factor BFC Bio-Fouling Control BSH Bundesamt f ̧r Seeschifffahrt und Hydrographie BWM Ballast Water Management BWMS Ballast Water Management System BWT Ballast Water Treatment cm Centimeter COPCs Chemicals of potential concerns CPVC Chlorinated polyvinyl chloride CTE Concentric Tube Electrode DBP Disinfection By-Products DC Direct current DOC Dissolved organic Carbon EC3 Effective concentration 3% EC50 Half maximal effective concentration EPA (U.S.) Environmental Protection Agency EU European Union FAC Free Available Chlorine FAH Free Available Halogen FDA U.S. Food and Drug Administration g Gram g/h Gram per hour GRP Glass Reinforced Plastic HAA Halogenated Acetic Acid HAZOP Hazard and Operability HMI Human-Machine Interface HOBr Hypobromous acid HOCl Hypochlorous acid IARC International Agency for Research on Cancer IMO International Maritime Organization IPCS International Programme on Chemical Safety kg Kilogram Koc Partition coefficient L Liter LC50 Median lethal dose LEL Lower explosive limit LNG Liquefied Natural Gas μm Micrometer m3/hr Cubic meters per hour mg Milligram MIC Microbially Induced Corrosion mV MillivoltMEPC 59/2/11 ANNEX

Page 5

I:\MEPC\59\2-11.doc NaOCl Sodium Hypochlorite N/D Not determined NIOZ Royal Netherlands Institute for Sea Research NOEC No-effect Concentration NTU Nephelometric Turbidity Unit ORP Oxidation Reduction Potential Pa Pascal PEC Predicted Environmental Concentration pH Measure of the acidity or alkalinity of a solution PLC Programmable Logic Controller PNEC Predicted No-effect Concentration POC Particulate Organic Carbon Pow Octanol-water Partition Coefficient PPE Personal protective equipment ppm Parts per million SCE Standard Electrode SWT Siemens Water Technologies TDS Total Dissolved Solids THM Trihalomethanes TNC Total Nitrogen Content TOC Total Organic Carbon TRC Total Residual Chlorine TRO Total Residual Oxidant TSS Total Suspended Solids UL Underwriters Laboratory US United States (of America) WHO World Health OrganizationMEPC 59/2/11 ANNEX Page 6

I:\MEPC\59\2-11.doc Index of tables

Table Description 3.1-1 Active Substance As Produced 3.1-2 Active Substance As Applied at Time Zero 3.2-1 Disinfection By-Products 4.1.1-1 Acute Aquatic Toxicity 4.1.2-1 Chronic Aquatic Toxicity 4.1.4-1 K oc s for the Active Substances and Relevant Chemicals 4.1.5-1 Log P ow s and BCFs for the Active Substances and Relevant Chemicals 4.2.1-1 Acute Mammalian Toxicity 4.2.2-1 Skin and Eye Effects 4.2.3-1 Repeated-Dose Toxicity Studies 4.2.4-1 Chronic Mammalian Toxicity Studies 4.2.5 Developmental and Reproductive Toxicity 4.2.6-1 Carcinogenicity 4.2.7-1 Mutagenicity/Genotoxicity 4.2.8-1 Toxicokinetics 4.3.1-1 Aerobic Degradation for Relevant Chemicals 4.3.1-2 Anaerobic Degradation for Relevant Chemicals 4.4-1 Physical and chemical properties of Active Substance and Treated Water 4.4-2 Commercially Availa ble Relevant Chemicals 4.5-1 Analytical Methods 5.4-1 Monitoring and Control Devices 5.8-1 Common fault conditions and troubleshooting guide 6-1 Hazard Identification for Active Substance and Relevant Chemicals 7.1.4-1 Persistence (P), Bioaccumulation (B), and Toxicity (T) Data for the Active Substances and Relevant Chemicals 7.2.1-1 DBP profile in ìwinterî wa ter after 5 days retention time 7.2.1-2 Results of tests with North Sea water 7.2.2-1 Results with chlori ne dose of 5.6 mg/L 7.2.2-2 Results with chlori ne dose of 2.7 mg/L 7.2.2-3 TRO after mixing treated water with untreated water 7.3.3-1 MAMPEC modelling results 7.3.3-2 Summary of PEC calculations for 80 ships 7.3.3-3 Disinfection By-Products 7.3.6-1 Predicted No-Effect Concentration (PNEC) for the Active Substances and Relevant Chemicals in Freshwater andSaltwater 7.4-1 TRO PEC/PNEC Ratios for Discharged Balla st Water in the Port of Rotterdam for 1 ship 7.4-2 TRO PEC/PNEC Ratios for Discharged Balla st Water in the Port of Rotterdam for 10 ships 7.4-3 TRO PEC/PNEC Ratios for Discharged Balla st Water in the Port of Rotterdam for 80 ships 7.4-4 DBP TRO PEC/PNEC Ratios for Discha rged Ballast Water in the Port of Rotterdam for 80 ships 8.1.2-1 Effect of chlorine concentration on corro sion of stainless stee l tubes in seawater 8.2.3-1 Comparison of Ballast Water Con centrations to Risk-Based CriteriaMEPC 59/2/11 ANNEX

Page 7

I:\MEPC\59\2-11.doc Index of figures

Figure Description 1-1 SiCURE TM BWM System 2.1-1 Dissolution of hypochlorous acid vs . pH at different temperatures 2.1-2 Ammonium and nitrate concentration in th e North Sea off the coast of Texel Island, The Netherlands 2.2-1 Log k (inactivation rate of poliovirus) vs. oxidation potential 2.2-2 ORP vs. FAH in synthetic s eawater with urea and glycine 2.2-3 ORP vs. Free Chlorine and water pH 2.2-4 ORP Readings in cooling water trea ted with chlorine on board LNG Carrier 2.3-1 3-D model of contai nerized SiCUREô BWMS 2.3-2 Concentric Tube Electrode of the Chloropac Æ cell 2.3-3 Chloropac Æ Generator 5.2-1 Filter used by SiCUREô BWMS 5.2-2 Block diagram of the SiCUREô BWMS 5.2-3 Typical SiCUREô BWMS Skid 7.2.1-1 ORP and chlorine dose vs. TSS 7.2.1-2 ORP, free, combined and total chlorine le vels in the ìwinterî North Sea water with 0 mg/l TSS treated with a chlorine dose of (a) 10 mg/l, (b) 5 mg/l and (c) to reach an ORP of about 750 mV (about 0.9 mg/l). 7.2.1-3 ORP, free, combined and total chlorine le vels in the ìwinterî North Sea water with 200 mg/l TSS treated with a chlorine dose of (a) 10 mg/l, (b) 5 mg/l and (c) to reach an ORP of about 750 mV (about 4.2 mg/l). 7.2.2-1 Halogen demand vs. contact period in logarithmic scales. 7.2.2-2 Model and experimental results for 5.6 mg/L dose 7.2.2-3 Model and experimental results for 2.7 mg/L dose 7.3.2-1 Test data and exponential decay model 7.3.3-1 Results of MAMPEC modeling for one ship, PEC TRO vs. TRO half-life at discharge TRO of 0.13 mg/l. Half-lif e axe is in a logarithmic scale 7.3.3-2 Results of MAMPEC modeling for one ship, PEC TRO vs. TRO half-life at discharge TRO of 0.55 mg/l. Half-lif e axe is in a logarithmic scale 7.3.3-3 Maximum concentration of TRO in the ha rbour calculated for 1, 10 and 80 ships for a half-life of 1 minute 7.3.3-4 Average concentration of TRO in the ha rbour calculated for 1, 10 and 80 ships for half-life of 30 minutes 7.3.3-5 Average concentration of TRO in the ha rbour calculated for 1, 10 and 80 ships for half-life of 1 hour 8.1.2-1 Corrosion Potential vs. Chlorine Concentration

Note : For figures 2.2-2, 2.2-3, 2.2-4, 2.3-1, 2.3-2, 2.3-3, 5.2-1, 5.2-2, 7.2.1-1, 7.2.1-2, 7.2.1-3 and 7.2.2-3, please refer to the confid ential part of the application.MEPC 59/2/11 ANNEX Page 8

I:\MEPC\59\2-11.doc 1 INTRODUCTION (CHLOROPAC  AND SICURE TM ñ A NATURAL EVOLUTION)

The Siemens SiCURE TM Ballast Water Management (BWM) Sy stem utilizes proven technology to filter out, oxidize and disinf ect aquatic invasive species (A IS) with Sodium Hypochlorite (NaOCl). NaOCl, a chlorine compound, has been used for many years to prevent marine growth in seawater piping and heat transfer systems of land-based, offshore and sh ipboard installations. It has been found that the most efficient me thod of hypochlorination is to produce sodium hypochlorite in-situ, electr olytically, on demand, utilizing the Si emens patented Concentric Tube Electrode (CTE) technology to produce NaOCl and inject the Sodium Hypochlorite into the seawater intakes. This technology is well known in the maritime industry under trademark Chloropac Æ

. Siemens Water Technologies is a leading prov ider of hypochlorination and electrochemical equipment designed to control bi ological fouling and corrosion wh erever seawater is used as cooling or process water.

A division of the Siemens Industry Solu tions group, Water Technologies capitalizes on world-class experience, technology, R&D supp ort and manufacturing facilities of the group, which provides innovative solutions and services fo r improved life cycle costs in processing and manufacturing industries and infrastructure.

The Siemens experience with Chloropac  and its shipboard installations worldwide has allowed Siemens to evolve the Chloropac  Marine Growth Prevention System into the SiCURE TM Ballast Water Management System.

The SiCURE TM BWM System that has several unique desi gn features is based on the Chloropac  Electrochlorination System developed to prevent marine organisms from fouling seawater piping and heat exchangers on board ships, offshore fac ilities, and land-based petrochemical and electric utilities. Biofouling control using Chloropac Æ technology has become extremely popular within the maritime industry since with Chloropac Æ control can be accomplished economically, reliably, eco-friendly and safely. The first Chloropac  electrochlorination system was patented and installed for commercial service in 1972. In 1975 the first skid mounted, hazardous area, Chloropac Æ plants were instal led on offshore production platforms in the North Sea and in 1984 a Hazardous Area Certificate (BASEE FA) was issued for Chloropac Æ Electrochlorinators.

Over 2,000 shipboard Chloropac  Systems have been installe d until today. These Chloropac  Electrochlorinators are protecting the circulating seawater systems on board oil tankers, container ships, LNG carriers, military ships and offshore facilities, from fouling of living organisms that can cause reduced seawater cooli ng flow rates, reduced heat exch anger efficiency, and increased fuel and maintenance costs.

The Chloropac  System electrolyzes seawater to pr oduce sodium hypochlorite, an ìActive Substanceî, on demand, in-situ directly from s eawater without the addition or mixing of any other chemicals.

The patent pending Siemens SiCURE TM BWM System utilizes a proven Chloropac  , Concentric Tube Electrode (CTE) Technology to produce s odium hypochlorite in sufficient quantity to completely eliminate AIS in the high volume ba llast water systems on board (see Figure 1-1).MEPC 59/2/11 ANNEX

Page 9

I:\MEPC\59\2-11.doc Figure 1-1: SiCURE TM BWM System

Unlike other BWM systems, SiCURE TM is not based on a fixed chlo rine dose. Rather, it is designed to provide a minimum required chlorine dose as demanded by the quality of the ballast water being treated. This is done employing fi ltration and proprietary disinfection control.

Pre-filtration of the ballast water is incorporated as part of the SiCURE TM BWM system to remove bigger AIS and sediments. This allows the electrochlorinator to produce less NaOCl, i.e. only the minimum required conc entration of NaOCl is produced.

In addition the Siemens expertise in disinfect ion of swimming pools, wastewater and cooling towers and the latest developments in Oxidati on Reduction Potential (ORP) technology led to the development of a proprietary control logic utilize d to regulate system parameters and provide the required treatment efficacy while minimizing any impact on the environment or the safety of the ship and its crew.

Proof-of-concept testing showed excellent results in eliminating viable organisms present in the water before treatment. This was achieved with a low generati on of disinfection by-products. The system is ready to be tested on a full, comme rcial scale in land-based and shipboard setting. Siemens believes that through the land-based and shipboard testi ng and the presentation of the test data we trust to show that the Siemensí SiCUREô Ballast Water Management System is in full compliance with regulation D-2 of the IMO Ballast Water Mnagement Convention, and will meet the standards and procedures of ìGuidelin es for approval of ballast water management systems (G8)î and will comply with the ìProce dure for approval of ballast water management systems that make use of Active Substances (G9)î.

Filtration combined with Sodium Hypochlorite produced in-situ a nd injected based on demand is the logical choice for ballast water management:

The main features of the SiCURE ô BWM system and process are:

- Filtration to remove zooplankton, some phytoplankton and larger sediments;

- Filtration of the ballast water further reduces the NaOCl dose requirements;MEPC 59/2/11 ANNEX Page 10

I:\MEPC\59\2-11.doc - Sodium Hypochlorite oxidation is well documented in shipboard and offshore applications;

- Sodium Hypochlorite has been demonstrat ed to have swift disinfection capabilities;

- Sodium Hypochlorite destroys within hours all AIS down to the bacteria level;

- Sodium Hypochlorite decays within hours;

- Sodium hypochlorite will reach environm entally acceptable levels during the ships voyage with little or no residual in the overboard discharge;

- Sodium Hypochlorite can be produced safely and economically in-situ. This eliminates the need to carry other unw anted possibly unsafe chemicals on board which will require special storage and handling by the crew;

- SiCURE TM BWMS Sodium Hypochlorite genera tors are low maintenance; CTE technology, utilizing centre taped cells to prevent stray curren ts in the ballast water;

- SiCURE TM BWMS modular design can accommodate any ballast water capacity; a singular system will be designed for a ba llast water flow from 200 to 3,000 m3/h;

- SiCURE TM BWMS can be supplied as indivi dual components to accommodate retro-fit applications on exis ting vessels as required; and

- SiCURE TM BWMS employs ìOn-Demandî hypochl orite dosing powered by Siemens proprietary ORP based control logic whic h allows automatic hypochlorite dosing depending on ballast water conditions. Th is minimizes residuals disinfection by-products (DBP) and corrosion.

Siemens is applying for Basic Approval of the SiCURE TM BWMS hypochlorination, its proprietary control technology combined with the filtration method of balla st water treatment in accordance with Procedure (G9) adopted by resolution MEPC.169(57).

2 DESCRIPTION OF THE SIEMENSí SiCURE TM BWM SYSTEM

Design of the SiCUREô BWMS was carried out with an emphasis on safety. Safety of the ship, its crew and the environment is related to the bi ocide dose used for disinfection, especially when chlorine based compounds are used. The dose level will affect such issues as corrosion, environmental risks to marine life and human ex posure. SiCUREô operation philosophy is based on on-demand dosing of chlorine produced in-situ fr om seawater. Biocide dosing is regulated to provide minimum required biocide levels to pr ovide disinfection, while reducing its residual, disinfection by-products (DBP) a nd corrosion to the ship. The control logic of the SiCUREô system is based on the principles develope d by a renowned microbiologist Dr. Ebba Lund discussed below in this section. These are the pr inciples currently used for safe disinfection of swimming pools and other recreatio nal facilities around the world.

In order to provide a required level of disinfection for a shipboard ballast wate r application, itís very important to understand the chemistr y and control of disinfection that are covered in this section.MEPC 59/2/11 ANNEX Page 11

I:\MEPC\59\2-11.doc 2.1 Basics of chlorine disinfection relevant to ballast water treatment

Chlorine found its use in many water treatm ent applications, such as disinfection of drinking/potable water, recreat ional water reservoirs (swimming pools and spas), industrial and municipal cooling towers, wastew ater, biofouling control of indus trial equipment in power and oil and gas industries, as well as for disinfection of seawater desalination equipment. Experience gained in these areas is invalu able for designing an effective and robust ballast water treatment system for shipboard use.

Chlorine dissolved in water instantly genera tes HOCl (hypochlorous acid) according to the equation (1):

Cl 2 + H 2 O ! HOCl + HCl (1)

So, whether gaseous chlorine or sodium, or calcium hypochlorite (also known as bleach) are being used as biocides, their germicidal effect is defined by the properties and effectiveness of the hypochlorous acid.

While the exact mechanism of the biocidal activity of hypochlorous acid is unknown, it is believed that it breaks through the cellular membranes and attack s cellular enzymes thus either killing the living organisms or rendering them non-viable.

When chlorine is dosed to the water it may get consumed by various inorganic, organic and biological compounds or elements present in water. For example, manganese and iron ions reduce chlorine to chloride ions. Therefore, the chlo rine dose which is requir ed for chlorine to be detected in the treated water is often called ch lorine demand. Furthermore, chlorine may react with certain compounds to create chloramines, also a biocide that is much weaker than HOCl. Additional dosing of chlori ne will lead to an increase in the chlorine concentration in water and will also lead to chlorine reacting with chlorami nes to produce nitrogen gas and chloride. Above certain levels, called breakpoint chlo rination, all chlorine present in the water will be in the form of free chlorine, often called Free Available Chlo rine (FAC) or Free Available Halogen (FAH). The breakpoint chlorination is used for treating ba llast water where extremel y high nitrogen content may be present. A sum of FAH and chloramines is usually referred to as Combined Chlorine.

Thus, chlorine dosing can be represented by the following diagram:

Dose = Chlorine Demand + Combined Chlorine

Combined Chlorine = Chloramines + Free Available Chlorine (HOCl).

Quite often Combined Chlorine is referred to as Total Residual Chlo rine or Total Residual Oxidant (TRO) and mistakenly used as a measure of the disinfection effi ciency. If both chloramines and FAH are present in water, it is FAH that provid es disinfection and not the combined chlorine. The germicidal efficiency of FAH is about 100 times greater than the efficiency of chloramines.

Moreover, hypochlorous acid is a ve ry weak acid with an ionizat ion constant within a range of 1.488x10 -8 at 0°C and 3.175x10 -8 at 30°C; when added to water it quickly undergoes disassociation in accordance with the following equation (2):

HOCl ↔ OCl - + H + (2)MEPC 59/2/11 ANNEX Page 12

I:\MEPC\59\2-11.doc Just like the chloramines, hypochl orite ions are a very weak oxidant, which makes undissociated HOCl the only biocide of importance.

Disassociation of HOCl depends on several factor s, such as water pH, temperature and ionic strength (or total dissolved solids ñ TDS), with the pH value being by far the most important factor influencing effectiveness of the disinfection tr eatment using chlorine . Figure 2.1-1 shows the HOCl fraction available for disinfection as a function of the water pH at the temperatures of 5°C and 20°C. Usually the pH value in potable water is maintained near 7.0 which makes about 80% of FAH available for disinfection as HOCl. The pH value in swimming pools is at 7.2 ñ 7.5, that would provide only 60 ñ 70% of FAH available for disinfection.

Implications of these tr ends for chlorination of ballast water could be quite significant. While most of disinfection a pplications are dealing with more or less consistent water quality, the quality of ballast water may vary significantly. For example, ballast water in the Great Lakes or coastal water in ports such as New York or Rottherdam, with an abundant supply of the river water, would be essentially a brackish wate r with pH very close to 7, while water in the Middle East and many other marine ports would be essentially s eawater with pH between 7.8 to 8.2. During algae bloom periods, the pH could be as high as 8.7 for an extended period of time, thus requiring a higher chlorine dose.

It should be noted though, that seawater contains somewhere between 35 to 65 mg/l of bromide. When chlorine is used for disinfection of seaw ater, it will oxidize bromide into hypobromous acid according to the Equation 3:

HOCl + NaBr ! NaCl + HOBr (3)

Hypobromous acid is also a strong biocide and it also dissociates in water similarly to the Equation 2. However, it s dissociation constant pK a is about 8.5 against chlorineís pK a of 7.5, thus HOBr is more stable than chlorine unde r alkaline pH values. While this helps in disinfecting seawater, the HOBr ava ilability within the pH range of 7.0 to 8.7 is still within a wide range of 50 to 99%.

pH, TDS, chloride/bromide ratio and temper ature of the ballast water may be changing significantly from season to season (e.g., due to ra infall) and from low to high tide within a single day. These changes will have a significant im pact on the availabili ty of undissociated hypohalogenous acid (HOCl and/or HOBr) and, as a re sult, the halogen dose required to provide the mandatory standards of treatment.

pH is very important for disinfection of water w ith halogens. However, other water conditions in different ports around the worl d are important as well, with the chlorine demand being one of them. 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

5 6 7 8 9 10 Water pH ValueSpecies Content

Fig.2.1-1: Dissolution of hypochlorous acid vs. pH Solid line - at 20°C, Dotted line - at 5°C HOCl OCl -MEPC 59/2/11 ANNEX Page 13

I:\MEPC\59\2-11.doc The chlorine demand of ballast water, taken on board either in fres hwater or seawater environments, is determined by inorganic and orga nic pollutants in water, as well as by the biological load. The pollut ants could be dissolved in water or be present in suspended solids of mineral or organic matter. The concentration of th ese pollutants is subject to variation as well. For example, Figure 2.1-2 shows seasonal variations in the concentration of ammonia and nitrites in the North Sea off the coast of the Netherlands.

Organics and other contaminants in fresh or sea water may significantly influence both th e chlorine demand and the ratio of Combined Halogens and FAC thus affecting the strength of the biocide dose and the effectiveness of the treatment as a whole.

In conclusion, ballast water c onditions, such as pH, TDS, temperature, chloride/bromide ratio, total suspended solids (TSS), total organic carbon (TOC ), total nitrogen content (TNC) have to be taken into account when chlorine treatment is used. More importantly, a dose required to provide an effective treatment of the ballast water has to be adjusted to those water condi tions. If the chlorine dose level is not sufficient, disinf ection will not be effective: if the chlorine dose selected is in excess of what is required, th is would impose problems, such as corrosion to the ballast tank materials and excessive formation of the DBP.

2.2 Control of disinfection

pH, total residual chlori ne and free residual chlorine analyses have been used extensively in water treatment to control water treatment processes. Using results of the pH and free residual chlorine analyses can theoretically be used to calculate a proper dose for disinfection of ballast water. However, these methods require daily maintenance and supply of reagents that may provide a burden to the ship crew. In the last 40 years, the oxidation-reduction potential (also known as redox potential or ORP) has gained popularity in controlling the effectiveness of the water treatment, especially for the disinfection of the swimming pools and spas.

Unlike residual chlorine analyzers that measure chlorine concentration and not its disinfection strength, ORP is used as a qualitative measure of the oxidizing potential (consumes electrons) or reducing potential (supplies elect rons) of water being treated.

The importance of ORP cont rol for water sanitation was established when in 1963 a world-renowned microbiologist Ebba Lund authored a paper (Lun d 1963) containing Figure 2.2-1. The graph shows that the inactivation rate of the Poliovirus is directly related to the oxidation potential. It also illustrates that inactivation rates are independent of the species of chlorine used (i.e. free vs. Fig.2.1-2: Ammonium and nitrate concentration in the North Sea off the coast of Texel Island, the Netherlands

Fig. 2.2-1: Log k plotted against the oxidation potential, where k is the velocity constant for the initial inactivation rate of poliovirus at 37°Cand pH 7.0

! Values obtained using partly purified virus

X Values obtained for inactivation by means of combined chlorine

! Values obtained for inactivation by means of free chlorineMEPC 59/2/11 ANNEX Page 14

I:\MEPC\59\2-11.doc combined chlorine). As ORP, measured in millivolts , rises, the rate of inactivation rises. Studies conducted later on Escherichia coli

, Salmonella sp. and Cryptosporidium sp. (Victorin et al . 1971, Carlson 1991, Rasmussen et al . 1994) to name a few, resulted in similar findings.

In the same paper, Ebba Lund has made another important observation derived from the experimental data, i.e. when the amount of re ductants is constant, th e redox potential and the residual chlorine concentration may both be used as parameters for the rate of inactivation, but when the amount of reductants (pollutants) is change d then only the redox potential may still be used.

The oxidation potential is a measure of the oxidi zing power of the oxidant, its ability to consume electrons. The stronger that ability of the oxida nt, the higher is the oxida tion potential (Siemens Stranco 2007). For example, an oxidation pot ential of free chlorine is 1.48 V, the oxidation potential of hypochlorite ion is just 0.84 V. The el ectrode of the sensor that is used to measure ORP is made from platinum or gold, which holds on very tightly to its electrons (noble metals). A sample of treated water is di rected across the sensorís electr ode tip for measurement of the water ORP. In clean water with no inorganic or organic load creati ng chlorine demand, the oxidizer in the water ìpullsî strongly on the electr ons in the platinum or gold tipped sensor. The higher the oxidation potential of the latter, the ha rder the oxidizer ìpullsî on the electrons, and the higher is the ORP reading.

In water with high chlorine demand, there is a ready supply of substances which provide electrons (these substances called reductant s). The oxidizer in the water draws its attention to this ready source of electrons and its oxidatio n strength towards viruses, bacter ia, algae, etc., diminishes. The ìpullî on the sensorís electrons is also re duced, that will result in a reduced ORP value.

In swimming pools the amount of re ductants (urea, uric acid, orga nics etc.) changes constantly with the bathersí use; in ballast water treatment it may change from port to port, from season to season at the same port or from the amount of TSS being pumped on board during the ballasting operation. Under these conditions, only the ORP can be used to en sure the inactivation rate of viruses and or bacteria while maintaining a cons tant concentration level of free and combined chlorine will not ensure the necessary inactiva tion rate. This also m eans that anything that reduces the ORP will reduce the inactivation rate.

This explains a variety of results reported in the literature where the effective Total Residual Chlorine (TRC) range was reported as low as be low 5 ppm (Nielsen et al, 2005) and as high as 40 ppm (State of Michigan 2002).

2.3 SiCUREô BWMS configuration

The Siemens SiCUREô BWMS employs a two-stage treatment process. The first stage is the filtration to remove zooplankton and a part of phytoplankton and sediments. The filter is installed directly into the ballast water ma in and has a bypass for ballast water discharge operations. The second stage is a proprietary disinfection with a bioc ide produced on board a ship in-situ from saltwater. Biocide that is predominantly a sodium hypochlorite solution produced electrochemically using a stand-alone el ectrochemical generator is injected into the ballast water on demand using proprietary control logic. On-demand biocide dosing is intended to significantly diminish corrosi on and disinfection by-products i ssues as well as to minimize residual biocide concentration in ballast water di scharge. Materials of construction are type approved CPVC pipe, FRP, titanium and Hastelloy- C. Filter is built of epoxy coated carbon steel with a 316 stainless steel scree n. Integration with the shipboa rd ballast system will include startup, shutdown, emergency shutdown and da ta acquisition comm unication protocols.MEPC 59/2/11 ANNEX Page 15

I:\MEPC\59\2-11.doc The SiCUREô BWM system is set up to operate automatically with minimal operator supervision. The unit is controlled by a Siemens Programmable L ogic Controller (PLC) programmed to initiate operation when all the syst em prerequisites for the operation are satisfied. The systemís mechanical equipment is:

- Automatic Backwash Seawater Inlet Filt er with a Backwash Pump (if required); - Seawater Booster Pump (if required); - Electrochemical Generator; - Degassing Equipment; - Biocide Dosing Pump; - Bio Fouling Analyzer Booster Pump; - ORP Control Loop; and - Automatic and Manual Valves.

The systemís electrical equipment is:

.1 Transformer/Rectifier; .2 System Control Panel; and .3 Motor Control Centre.

The core of the system is its Chloropac Æ electrochemical generator. The electrolyzer consists of a pre-determined number of cells arranged in se ries. The cells are housed in an enclosure that provides additional personnel protection.

3 IDENTIFICATION OF THE PREPARATION, ACTIVE SUBSTANCE, BY-PRODUCTS AND RELEVANT CHEMICALS (G9: 4.1)

3.1 Active Substances

SiCUREô BWM system uses seawater to produ ce biocides in-situ using principles of electrochemistry and then injects them into the ballast water in ìon-demandî quantities required to achieve a certain redox potential (oxi dation strength) of the ballast water.

At the outlet of the electrochemical generator, seawat er will contain several products of electrochemical reactions taking place at the anode and cathode surf aces of the CHLOROPAC ge nerator. These are hypochlorous acid (HOCl) in equilib rium with hypochlorite ion (OCl - ), hypobromous acid (HOBr) in equilibrium with hypobromous ion (OBr - ), certain short-life oxygenated chemical compounds and oxygen gas (O 2 ) generated at the a node and hydrogen gas (H 2 ) generated at the cathode.

As hydrogen gas is a safety hazard and should not be allowed accumulating in the ballast tanks, the SiCUREô system produces biocides not in th e main ballast water flow, but rather in a side-stream flow of about 5.5 or 11 m 3 /h. The side-stream flow is se lected based on the size of a system and is independent of the main balla st water flow. Resul ting ìActive Substance Concentrateî or ìActive Substance as Producedî is then directed into the degas tank where it is allowed to remain for a minimum of 5 minutes to remove entrained hydrogen and oxygen gases that are then diluted with air to the below LEL and safely vented into the atmosphere. At the same time, all short-lived a nd highly reactive oxyge nated species, possib ly including hydrogen peroxide and ozone, present in the stream will decompose. For example, hydrogen peroxide will be reduced to water by free av ailable chlorine and ozone will decompose into oxygen gas with chlorine acting as a catalyst. Therefore, these oxy genated species will not be considered as either Active Substances or Relevant Chemicals.MEPC 59/2/11 ANNEX Page 16

I:\MEPC\59\2-11.doc The concentration of HOCl and HOBr, as produ ced, will depend on a size of the system. For example, the systems used for treating 200 m 3 /h and 1,000 m 3 /h will use the same side-stream flow of 5.5 m 3 /h, however they will be producing biocide at the concentration levels of up to 300 mg/l and 1,500 mg/l, correspondingly.

Further, since the SiCUREô BWMS employs vari able biocide dosing, vari able dose is achieved by maintaining the constant side-stream flow an d varying the DC current from the transformerrectifier to meet a specific bi ocide demand. Therefore, the bioc ide concentration in the side stream will vary.

Furthermore, the concentration of HOCl and HOBr and their ratio to the oxygen gas as a byproduct may vary significantly depending on the sa linity and temperature of seawater and the current density (current over the anode surface area) applied to the anodes For example, at 15 ñ 30°C and in seawater with sodium chloride content of 25 ñ 35 g/l and at low to moderate current densities, as much as 90% of the curre nt is consumed to produce HOCl and HOBr. At low temperatures, such as 2 to 12°C and in brackish water and at high current densities in excess of 2,000 A/m2, as low as 50 to 60% of the current is used for HOCl/HOBr generation.

Therefore, the concentration of biocides as produced will vary. However, their maximum concentration will be limite d by the imposed DC current and voltage boundaries.

Hydrogen gas and oxygen gas are completely remove d in the degas tank, therefore they will be considered as by-products and not Relevant Chemi cals. The list of Active Substances as produced by the SiCUREô BWMS and their expected con centration ranges are presented in Table 3.1-1.

Table 3.1-1: Active Substances as produced

Composition of Active Substances As Produced Component Chemical Name CAS Number Concentration, mg/l AS, RC or Other Hypochlorous Acid (as sodium hypochlorite) 7681-52-9 100 ñ 1,500 AS

Hypobromous Acid (as sodium hypobromite) 13824-96-9 30 ñ 65 AS

Oxygenated Species N/A 0 AS Oxygen 7782-44-7 None By-product Hydrogen 1333-74-0 None By-product

According to the proof-of-concept testing car ried out by Siemens, SiCUREô BWMS biocide dosing levels controlled by the ORP does not exceed 6 mg/l. Therefore, the maximum concentration of the biocide injected into the ballast water will be at 6 mg/l.

While most of the biocides produced by the SiCUREô BWMS are comp rised of HOCl, when biocide is mixed with the ballast water th e spectrum of Active Substances may change significantly. In particular, HOCl and HOBr ratio in ballast water is a subject to the quality of the water being treated, especially its sodium bromide content. It is expected that in fresh water the predominant biocide species will be HOCl. Considering a maximum biocide dose level of 6 mg/l and a typical concentration of bromide ions in seawater at 35 ñ 65 mg/l, it is expected that in seawater a predominant biocide species will be HOBr. A mix of HOBr and HOCl may be expected in brackish water with bromide content less than 6 mg/l.MEPC 59/2/11 ANNEX Page 17

I:\MEPC\59\2-11.doc Both HOCl and HOBr are strong oxidizers and hal ogenation agents and w ill react with certain nitrogen compounds such as amm onia, urea, aminoacids, etc., pr esent in fresh or salt water generating chloramines and/or bromamin es, collectively called haloamines.

Haloamines are also oxidizers, although not as strong as HOCl or HOBr, and have to be considered as Active Substances.

When chlorine and bromine based compounds are an alyzed in the treated water, they typically analyzed together and reported as Free Availa ble Halogen (FAH) for a sum of HOCl and HOBr or as Total Residual Oxidant (TRO) for a sum of HOCl , HOBr, chloramines and bromamines. Therefore, the Active Substance in the treate d ballast water using SiCURE BWMS process should be characterized as TRO. It is expected that in fresh wa ter TRO will be mainly comprised of HOCl and chloramines and in salt water ñ of HOBr and bromamines.

It is virtually impossible to provide a further breakdown for the concentr ations of chloramines and bromamines in TRO as these are unstable compounds and there are no calibration standards available to ensure their reliable analysis.

Table 3.1-2 below provides an estimate of the rele vant concentration of TRO and its constituents in the treated ballast water at the time zero after their injection into the ballast water.

Table 3.1-2: Active Substance as applied at time zero (T0)

Active Substance As Applied (at Time Zero (T0)) Component Chemical Name CAS Number Concentration, mg/l AS, RC or Other

Freshwater Saltwater
TRO * : ≤ 6.0 ≤ 6.0 AS Hypochlorous acid ≤ 6.0 0 AS Hypobromous acid ≤ 1.0 ≤ 6.0 AS
Chloramines ** Not available 0.5 0 AS
Bromamines *** Not available 0 0.5 AS

* A m i x o f F AH

, co m b i n ed c h l o r i ne, c o m b i n ed b r o m i n e, i f a n y , m easure d a s e q u i va l e n t c h l o r i ne

** A mix of monochloramine, dichloramine and nitrogen trichloride

*** A mix of monobromamine, dibromamine and nitrogen tribromide

3.2 Relevant Chemicals

Siemens has identified trihalomethanes (THM), haloacetic acids (HAA) and sodium bromate disinfection by-products as Releva nt Chemicals. Depending on a so urce of ballast water (fresh water or seawater) composition of these Relavant Chemicals will vary. A selected list of Relevant Chemicals is presented in the table be low. A more detailed list of disinfection by-products tested by Siemens over the duration of its proof-of-concept study is provided in section 7.2 ìEvaluation of Treated Ballast Wate rî. Siemens acknowledges that the referenced below list for Relevant Chemicals may be incomplete at this point and will be thoroughly investigated during land-based a nd shipboard testing. Concentration levels of certain Relevant Chemicals presented in the tabl e were obtained during laboratory tests with water from the North Sea (saltwater) by simulating SiCUREô BWM system, therefore the data provided for fresh water are our best estimates.MEPC 59/2/11 ANNEX Page 18

I:\MEPC\59\2-11.doc Table 3.2-1: Disinfection by-products

List of potential by-products produced in ballast water 2
Concentration, μg/l Chemical Name Formula Molecular Weight CAS Number

Fresh water 1 Salt water (bio)degradation rate or half-life

Trihalomethanes:

Trichloromethane CHCl 3 119.38 67-66-3 < 90 0 3 From no decay to 28 days
Dibromochloromethane CHBrCl 2 208.29 124-48-1 0 < 3 No decay
Tribromomethane CHBr 3 252.77 75-25-2 0 < 90 No decay

Haloacetic acids:

Dichloroacetic acid C 2 H 2 Cl 2 O 2 128.94 79-43-6 < 30 < 3 > 60 days
Trichloroacetic acid C 2 HCl 3 O 2 163.39 76-03-9 < 33 0 > 60 days
Dibromoacetic acid C 2 H 2 Br 2 O 2 217.86 631-64-1 0 < 50 > 60 days
Tribromoacetic acid C 2 HBr 3 O 2 296.76 75-96-7 0 < 60 > 60 days

Sodium Bromate NaBrO 3 150.9 7789-38-0 0 < 80 > 60 days

Note : 1

ñ Estimate. There were no tests performed to date w ith the fresh water. This will be addressed during land-based and shipboard testing. 2

ñ D u r i ng la n d- b ase d testi ng h a lo g e n acet on itrile c o m p ou nd s will be als o i n clu d e d f o r a n alysis a nd b e added to the list of potential Relevant Chemicals, if necessary. 3

– Indicates c onc e n tration below t h e a n alytical dete c ti on l i m i t s . See s e c ti on 4

. 5 f o r t h e de t ec ti o n l i m i ts.

4 DATA-SET FOR ACTIVE SUBSTANCES AND PREPARATIONS (G9: 4.2)

4.1 Data sets on effects on aquatic plan ts, invertebrates and fish (G9: 4.2.1.1)

4.1.1 Acute aquatic toxicity

Acute toxicity data for both the Active Substances and Relevant Chemicals we re selected to conform where possible with OECD Guidelines 203 (adopt ed 17 July 1992), 202 (a dopted 13 April 2004), and 201 (adopted 23 March 2006), fo r fish, crustaceans, and algae, respectively. In some cases toxicity data could not be found that followed th e OECD Guidelines. Thus, some toxicity data were taken that utilized other acce ptable test procedures. In addi tion, selected data that did not meet OECD Guidelines or other accepted testing procedures were included to provide an indication only of potential toxicity. The deviations from OECD Guidelines are given in the footnotes of Table 4.1.1-1. The data given in Table 4.1.1-1 ar e the lowest toxicity values found in the literature for each of the test substanc es for fish, crustaceans, and algae.

The literature summarized below fo r acute toxicity shows that TRO and HOCl are more toxic to fish and crustaceans relative to brom ate, THMs, and HAAs (Table 4.1.1- 1). For example, the acute toxicity of TRO and HOCl to fish and crustacea ns ranges from 0.032 up to 0.143 mg/L. The acute toxicity values of bromate, THMs, and HAAs are 2-3 orders of magnitude higher. No acceptable exposure data for algae (minimum 72-hour exposure; OE CD 201 Guideline requ irement) were foundMEPC 59/2/11 ANNEX Page 19

I:\MEPC\59\2-11.doc for TRO and HOCl. The data for algae included in the table to provide an indication only of potential toxicity also suggests that TRO is more toxic to alga e than bromate, THMs, and HAAs.

No relevant ecotoxicity data wa s found for HOBr because of the co mplexity of HOBr chemistry. It is believed that HOBr produced from HOCl and NaBr in saltwater has a short life and decomposes producing bromide and bromates. Siem ens will investigate this further and carry out ecotoxicity testing with HOBr prior to Final Approval.

Relative to the Active Substances, br omate is not very toxic to fish and crustaceans. The LC50 for the fish was 31 mg/L and the EC50 for the crustacean was 176 mg/L. No data were found for algae which met OECD 201 Guidelines. Chloroform and bromoform were approximately 2-3 orders of magnitude less toxic than TRO. The fish data fo r dibromochloromethane (34 mg/L) also indicates that this THM is also much less toxic than TRO.

The crustacean value of 106 mg/L for dichloroacetic acid indicates that this haloacetic acid is much less toxic than TRO (Table 4.1.1-1). Trichloroacetic acid ( 500-2000 mg/L) is 3-5 orders of magnitude less toxic than TRO. A value of 69 mg/L for a fish exposed for 96 hours to dibromoacetic acid is present in U.S. EPAís ECOTOX database; however, the value is actually for dibromoacetamide (Mayes et al. , 1985). No verifiable data we re found in the literature for the acute toxicity of dibromoacetic acid and tribromoacetic acid.

Table 4.1.1-1: Acut e aquatic toxicity a

Test Substance F C A Species Test Type LC50/ EC50 mg/L NOEC mg/L Reference/ Comments

Active Substances

F Oncorhynchus mykiss 15-d survival 0.059 N/A Fisher et al. (1999)

C Daphnia magna 48-h survival b 0.032 N/A Fisher et al. (1999) TRO (Freshwater)

A Natural phytoplankton 47-h change in Chl a c (<,0.1) NA Brooks and Liptak (1977)

F Menidia beryllina 96-h survival 0.143 N/A Fisher et al. (1999)

C Mysidopsis bahia 96-h survival d 0.062 N/A Fisher et al. (1999) TRO (Saltwater)

A Dunaliella primolecta 24-h growth e (0.075) N/A Videau et al. (1979)

F Oncorhynchus mykiss 96-h survival 0.032 N/A Thatcher (1978)

C Americamysis bahia 7-d survival 0.144 N/A Fisher et al. (1994) HOCl

A Porphyra yezoensis 10-d growth 1.400 N/A Maruyama et al. (1988)

F *) No data found in literature

C *) No data found in literature HOBr

A *) No data found in literatureMEPC 59/2/11 ANNEX Page 20

I:\MEPC\59\2-11.doc Test Substance F C A Species Test Type LC50/ EC50 mg/L NOEC mg/L Reference/ Comments

Relevant Chemicals

F Morone saxatilis 96-h survival 31 N/A Richardson et al. (1981)

C Neomysis awatschensis 24-h survival g 176 N/A Crecelius (1979) Bromate

A *) No data found in literature

F Lepomis macrochirus 96-h survival 14 N/A Anderson et al. (1979)

C Artemia salina 24-h survival g 30 N/A Foster and Tullis (1984) Chloroform

A Scenedesmus subspicatus 48-h growth h (950) N/A Kuhn and Pattard (1990)

F Cyprinodon variegatus 96-h survival 18 2.9 Heitmueller et al. (1981)

C Daphnia magna 48-h immobilization 46 N/A LeBlanc, G.A. (1980) Bromoform

A Skeletonema

costatum 96-h growth inhibition 12.3 N/A U.S. EPA (1978)

F Cyprinus carpio 72- to 120-h egg fertilization to hatch i 34 N/A Mattice et al. (1981)

C *) No data found in literature Dibromochloromethane

A *) No data found in literature

F *) No data found in literature

C Daphnia magna 24-h immobilization j 106 N/A Trenel and Kuhn (1982) Dichloroacetic acid

A *) No data found in literature

F Pimephales promelas 96-h survival 2000 N/A Dennis et al. (1979)

C Daphnia magna 48-h immobilization 2000 N/A Dennis et al. (1979) Trichloroacetic acid

A Chlorella pyrenoidosa 72-h growth N/A 500 Huang and Gloyna (1968)

F *) No data found in literature

C *) No data found in literature Dibromoacetic acid

A *) No data found in literatureMEPC 59/2/11 ANNEX Page 21

I:\MEPC\59\2-11.doc Test Substance F C A Species Test Type LC50/ EC50 mg/L NOEC mg/L Reference/ Comments

F *) No data found in literature

C *) No data found in literature Tribromoacetic acid

A *) No data found in literature

F = Fish; C = Crustacean; A = Algae. *) Siemens will obtain data executing own toxicity tests for Final Approval

a Data shown in parenthesis do not meet OECD Guid elines or other accepted testing procedures but were included to provide an indication only of potential toxicity. b Study did not meet the OECD 202 Guidelines because the test evaluated survival rather than immobilization at 48 h. However, the test did meet U.S. EPA regulatory test re quirements (Test Method 2021 .0) for measuring the acute toxicity of effluents an d receiving waters to Daphnia magna (U.S. EPA, 2002a).

c Study did not meet OECD 201 Guidelines because the test evaluated a change in chloro phyll at 47 h rather than growth at 72 h. d Study did not meet OECD guide lines because the test evaluated survival at 96 h rather than immobilization at 48 h. However, the test did meet U.S. EPA regulatory test re quirements (Test Method 2007 .0) for measuring the acute toxicity of effluents an d receiving waters to Mysidopsis bahia (U.S.EPA, 2002a).

e Study did not meet OECD 201 Guidelines because the test ev aluated a growth at 24 h rather than growth at 72 h.

g Study did not meet OECD 202 Guidelin es because the test evalua ted survival at 24 h ra ther than immobilization at 48 h. However, the test did meet U.S. EPA regulatory test requirements (Test Method 2002.0) for measuring the acute toxicity of effluents and receiving wate rs to a representative crustacean (U.S.EPA, 2002a). h Study did not meet OECD 201 Guidelines because the test ev aluated growth at 48 h rather than growth at 72 h. i Hatching of the embryos varied from 72 to 120 h; thus, a definitive exposure period for the LC50 could not be established. Test did not meet OECD 203 Guidelines; however, the test did meet U.S. EPA regulatory test requirements (Test Method 10 01.0) for measuring the chronic toxicity of effluents and receiving waters to a freshwater fish (U.S.EPA, 2002b). j Study did not meet OECD 202 Guidelines because the test evaluated immobilization at 24 h rather than immobilization at 48 h. However, the test did meet U.S. EPA regulatory test requirements (Test Method 2002.0) for measuring the acute toxici ty of effluents and receiving waters to a representa tive crustacean (U.S.EPA, 2002a).

4.1.2 Chronic aquatic toxicity

Chronic toxicity data for both the Active Substa nces and Relevant Chemicals were selected to conform where possible with OECD Gu idelines 210 (adopted 17 July 1992), 211 (adopted 3 October 2008), and 201 (adopted 23 Ma rch 2006), for fish, crustaceans, and algae, respectively. In some cases toxi city data could not be found that followed the OECD Guidelines. Thus, some toxicity data were us ed that utilized other acceptable test procedures. In addition, selected data that did not meet OECD Guidelines or other accepted testing procedures were included to provide an indication only of potential toxicit y. The deviations from OECD Guidelines are given in the footnotes of Table 4.1.2-1. The data given in Table 4.1.2-1 are the lowest toxicity values found in the literature for each of the test substances fo r fish, crustaceans, and algae.

The literature summarized below for chronic to xicity shows that TRO and HOCl more toxic to fish and crustaceans relative to bromate, THMs, and HAAs. The chronic toxicity of TRO to fish is 0.04 mg/L. The chronic toxicity of TRO to crustaceans is 0.012 mg/L. The chronic toxicity values of bromate, THMs, and HAAs are 2 to 4 orders of magnitude higher. No acceptable OECD 201 guideline exposure data for algae were found for TRO. The data for algae included in the table to provide an indication only of poten tial toxicity also suggests that TRO is moreMEPC 59/2/11 ANNEX Page 22

I:\MEPC\59\2-11.doc toxic to algae than bromate, THMs, and HAAs. The chronic HOCl 10-d EC50 value (growth) of 1,400 mg/L for the red alga is quite high relati ve to the algal NOEC TRO values. No chronic data were found in the literature for hypobromous acid.

Relative to the Active Substances, bromate is not very toxic to algae (8 mg/L). The NOEC for the fish (50 mg/L) which did not meet OECD 211 Guidelines for a minimum 28-day post-egg exposure also indicates that bromate may not highly toxic to fish relative to the Active Substances. Chloroform, which ranged from 1.5 up to 216 mg/L, is approxi mately 2 to 3 orders of magnitude less toxic than TRO to fish, crusta ceans, and algae. The NOEC for bromoform to an alga was 10 mg/L which is less toxic than TRO. No acceptable data could be found for the chronic toxicity of bromoform to fish and crustaceans. No chr onic data could be found for fish, crustaceans, or algae exposed to dibromochloromethane.

Only two chronic values were found in the literatur e for the four haloacetic acids under consideration in this dossier. An EC3 of 1485 mg/L was found fo r an alga exposed to di chloroacetic acid. The 7-day algal cell proliferati on test does not meet the OECD 201 Guidelines which require a minimum 72-hour growth measurement as th e endpoint. A NOEC of 200 mg/L has been reported for an alga exposed to trichloroacetic ac id. This toxicity threshold value also does not meet the OECD 201 Guidelines which require a minimum 72-hour growth measurement as the endpoint. Although the two haloacet ic acid algae values do not meet OECD 201 Guidelines, the values are given in Table 4.1.2-1 as an indicati on of potential chronic to xicity. No fish or crustacean chronic data were found for dichloroacetic acid or tric hloroacetic acid. No chronic toxicity data of any type were found for dibromoacetic acid or tribromoacetic acid.

Table 4.1.2-1: Chronic Aquatic Toxicity a

Test Substance F C A Species Test Type LC50/ EC50 mg/L NOEC mg/L Reference/ Comments

Active Substances F Ictalurus punctatus 134-d growth b N/A (0.005) Hermanutz et al. (1990) C Gammarus pseudolimnaeus 70-d fecundity N/A 0.012 Authur et al. (1975) TRO (Freshwater) A Natural algae 24-d inhibition of biomass c N/A (0.079) Pratt et al. (1988) F Menidia peninsula 32-d egg to posthatch N/A 0.04 Goodman et al. (1983) C Panaeus kerathurus 7-d growth/moulting d N/A (0.079) Saroglia and Scarano (1979) TRO (Saltwater)

A Natural phytoplankton 21-d reduction in cell density c N/A (0.001) Sanders et al. (1981) F Oncorhynchus kisutch 23-d survival e N/A 0.042 Holland et al. (1960) C Americamysis bahia 7-d reproduction d N/A 0.048 Fisher et al. (1994) HOCl

A No data found in literatureMEPC 59/2/11 ANNEX Page 23

I:\MEPC\59\2-11.doc Test Substance F C A Species Test Type LC50/ EC50 mg/L NOEC mg/L Reference/ Comments

F No data found in literature C No data found in literature HOBr

A No data found in literature Relevant Chemicals F Morone saxatilis 10-d survival f (93) (50) Richardson et al. (1981) C No data found in literature Bromate

A Isochrysis galbana 7-d growth inhibition N/A 8 Erickson and Freeman (1978) F Oryzias latipes 9-month growth N/A 1.5 Toussaint et al. (2001) C Daphnia magna 21-d reproduction N/A 13 Kuhn et al. (1989) Chloroform

A Skeletonema

costatum 5-d reduction in cell volume 477 216 Cowgill et al. (1989) F No data found in literature C No data found in literature Bromoform

A Selenastrum capricornutum 96-h growth inhibition N/A 10 U.S. EPA (1978) F No data found in literature C No data found in literature Dibro m ochlor ome thane A No data found in literature F No data found in literature C No data found in literature Dichloroacetic acid A Scenedesmau subspicatus 7-d cell proliferation g (1485 EC3) N/A Trenel and Kuhn (1982) F *) No data found in literature C *) No data found in literature Trichloroacetic acid A Scenedesmus quadricauda 7-d growth threshold h (200) OECD SIDS (2008)MEPC 59/2/11 ANNEX Page 24

I:\MEPC\59\2-11.doc Test Substance F C A Species Test Type LC50/ EC50 mg/L NOEC mg/L Reference/ Comments

F *) No data found in literature C *) No data found in literature Dibromoacetic acid A *) No data found in literature F *) No data found in literature C *) No data found in literature Tribromoacetic acid A *) No data found in literature

F = Fish; C = Crustacean; A = Algae. *) Siemens will obtain data executing own toxicity tests for Final Approval

a Data shown in parenthesis did not meet OECD Guide lines or other accepted tes ting procedures but were included to provide an indication only of potential toxicity. b Study did not meet OECD 210 Guidelines because the te st was initiated with juven iles rather than the egg stage.

c Study did not meet OECD 201 Guid elines because the test did not have control culture biomass data. d Study did not meet OECD 211 Guide lines because the test was not a 21-d reproduction test. The test did follow a portion of the protocol of the U.S. EPA OPPTS 850.1350 mysid chronic toxicity test (U.S. EPA, 1996); however, moulting was only observed for 7 days rather than the minimum of 28 days.

e Study did not meet OECD 210 Guide lines because the test exposure was 23 days rather than the required minimum of 28 days. f Study did not meet OECD 210 Guidelines because the test was initiated with 4-d old larvae (not eggs) and the post-hatch exposure was 10 days rather than the required minimum of 28 days.
g Study did not meet OECD 201 Guidelin es because the test used cell prolif eration and as an endpoint rather than growth. h Study did not meet OECD 201 Guide lines because the test used toxicity threshold as the endpoint rather than growth.

4.1.3 Endocrine disruption

No reports were found in the literature that indicated the Active Subs tances (TRO) may be endocrine disrupters in aquatic organisms. Likewise, no reports were found that indicated the listed in dossier trihalomethanes, haloacetic acids, and bromate may be endocrine disrupters in aquatic organisms.

4.1.4 Sediment toxicity

Neither the Active Substances nor the Relevant Chemicals appear to have the potential to be adsorbed to sediments to a significant extent based on the adsorption coefficients (Kocs) for the chemicals summarized below. All of the Kocs were <500 L/kg which indicate that the chemicals would not readily partition to sediment and thus be of concern to benthic organisms residing in the sediment. Furthermore, as shown in the ne xt section (4.1.5), all of the log Pows for the Active Substances and Relevant Chemicals are <3 which indicate that significant bioconcentration/bioaccumulation (< 100 L/kg wet weight for the whol e organism at 6% fat) of the chemicals will not occur.MEPC 59/2/11 ANNEX Page 25

I:\MEPC\59\2-11.doc Table 4.1.4-1: K oc s for the Active Substances and Relevant Chemicals

Chemical K oc (L/kg) Reference
Active Substances TRO 14.3 EPI Suite (2007) Hypochlorous acid 14.3 EPI Suite (2007) Hypobromous acid 14.3 IMO (2008d)
Relevant Chemicals THM - Chloroform 40 Howard (1990) THM -Dibromochloromethane 95-468 Howard (1990) THM -Bromoform 35 TOXNET (2008) HAA -Dichloroacetic acid 75 TOXNET (2008) HAA -Trichloroacetic acid 130 TOXNET (2008) HAA -Dibromoacetic acid 1.90 IMO (2008d)
HAA-Tribromoacetic acid 2.74 EPI Suite (2007)
Bromate 2.7 x 10 -8 IMO (2008c)

4.1.5 Bioavailability/biomagnification/bioconcentration

The log Pows for the Active Substa nces and Relevant Chemicals ar e all <3 which indicate that significant bioconcentration/bioa ccumulation (<100 L/kg wet weight for the whole organism at 6% fat) of the chemicals will not occur. Li kewise, the BCFs also show that the potential for significant bioconcentrati on/bioaccumulation is small in aquatic organisms. Little biomagnification should occur in a food web since the chemicals are not readily bioconcentrated/bioaccumulated.

Table 4.1.5-1: Log P ow s and BCFs for the Active Substances and Relevant Chemicals

Chemical log P ow BCF (L/kg) Reference Active Substances TRO -0.87 -2.19 EPI Suite (2007) Hypochlorous acid -0.87 -2.19 EPI Suite (2007) Hypobromous acid -1.03 1.24 IMO (2008e) Relevant Chemicals THM -Chloroform 1.97 3.3-10.4 Howard (1990) THM -Dibromochloromethane 2.24 0.74-1.47 Howard (1990) THM -Bromoform 2.40 14 TOXNET (2008) HAA -Dichloroacetic acid 0.92 3 TOXNET (2008) HAA -Trichloroacetic acid 1.33 0.4 - <1.7 TOXNET (2008) HAA -Dibromoacetic acid 0.70 0.41 IMO (2008c) HAA-Tribromoacetic acid 1.71 0.39 EPI Suite (2007) Bromate -7.18 3.7 x 10 -7 IMO (2008c)

4.1.6 Food web/population effects

Little biomagnification and persis tence in aquatic and mammalian food webs is anticipated from the Active Substances or Relevant Chemicals. This conclusion is based on the low Kocs and log Pows of the chemicals. All of the Kocs for both the Active Substances and Relevant ChemicalsMEPC 59/2/11 ANNEX Page 26

I:\MEPC\59\2-11.doc (section 4.1.4) are <500 L/kg which indicate that the chemicals would not readily absorb to sediment and thus be of concern to benthic populations and their food webs.

The log Pows for the Active Substa nces and Relevant Chemicals ar e all <3 which indicate that significant bioconcentration/bioa ccumulation (<100 L/kg wet weight for the whole organism at 6% fat) of the chemicals will not occur. Likewise for the chemicals that have established BCFs, the BCFs also show that little bioconcentration/bioaccumu lation will occur in aquatic organisms. Little biomagnification should occu r in an aquatic food webs and bird/mammalian food webs since the chemicals are not readily bioconcentrated/bioaccumulated.

4.2 Data on mammalian toxicity (G9: 4.2.1.2)

The following tables summarize data on mammalian toxicity for a variety of endpoints. The information used in these tables is mainly from toxicology summaries performed by the International Programme on Chemical Safety (which is a cons ortium including the World Health Organization and United Nations Environment Programme), a nd United Sates sources, such as the National Library of Medicine. In some cas es, information from Material Safe ty Data Sheets were compiled. The studies discussed in thes e toxicology summaries represen t valid and reproducible data.

4.2.1 Acute mammalian toxicity

Table 4.2.1-1 lists LD50s for the various chemicals. LD50 is the lethal dose that kills 50% of the animals tested, and is a measure of acute toxic ity. The lowest LD50s noted are for chloroform (36 to 2,000 mg/kg) and bromate (280 to 495 mg/ kg). The LD50s for the other chemicals are mainly above 1,000 mg/kg.

Table 4.2.1-1: Acute mammalian toxicity

Chemical Exposure Route Species Value Range Reference/Comments Hypochlorous acid a. oral LD50 a. Rat a. 8,900 mg/kg HSDB, 2008

b. oral LD50 b. Mouse b. 5800 mg/kg Chloramine Oral LD50 Rat 935 mg/kg Mallinkrodt Baker MSDS, 2006 Hypobromous acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Chloroform a. oral LD50 a. Rat a. 450 to 2,000 mg/kg IPCS, 2004 b. oral LD50 b. Mice b. 36-1366 mg/kgDibromochloromethane a. oral LD50 a. Male mice/ female mice a. 800 mg/kg/ 1,200 mg/kg IPCS, 2000

b. oral LD50 b. Male rats/ female rats b 1186 mg/kg/ 848 mg/kgMEPC 59/2/11 ANNEX Page 27

I:\MEPC\59\2-11.doc Chemical Exposure Route Species Value Range Reference/Comments

Bromoform a. oral LD50 a. Male mice/ female mice a. 1,400 mg/kg/ 1,550 mg/kg IPCS, 2000

b. oral LD50 b. Male rats/ female rats b. 1,388 mg/kg/ 1,147 mg/kg Dichloroacetic acid oral LD50 Rats and mice 4,500 and 5,500 mg/kg of body weight in rats and mice IPCS, 2000

Trichloroacetic acid oral LD50 Rats and mice 3,300 mg/kg of body weight in rats and 4,900 mg/kg of body weight in mice IPCS, 2000

Dibromoacetic acid oral LD50 Rats 1,737 mg/kg of body weight IPCS, 2000

Tribromoacetic acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromate oral LD50 Rats, mice and hamsters 280 to 495 mg/kg of body weight IPCS, 2000

4.2.2 Skin, eye and sensitization effects

Table 4.2.2-1 notes whether direct application of the chemicals can cause irritation to the skin and eyes. No data could be found for sensitization effects for any of the chemicals. As shown in Table 4.2.2-1, all of the chemicals have the potential to cause irr itation to the skin and eyes at sufficient concentrations. Wher e effects concentrations are pr ovided, they are higher than concentrations typically found in treated ballast water.

Table 4.2.2-1: Skin and Eye Effects

Chemical Skin Eye Reference/Comments Hypochlorous acid Skin hyperplasia in mice at high concentrations; >300 mg/L Irritating to the eye IPCS, 2000 HSDB, 2008

Chloramine No skin hyperplasia observed in mice at concentrations up to 1,000 mg/L Irritating to the eye IPCS, 2000 HSDB, 2008

Hypobromous acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Chloroform Irritating to the skin Irritating to the eye IPCS, 2004MEPC 59/2/11 ANNEX Page 28

I:\MEPC\59\2-11.doc Chemical Skin Eye Reference/CommentsDibromochloromethane Irritating to the skin Irritating to the eye Aldrich Chemical MSDS

Bromoform Irritating to the skin Irritati ng to the eye Mallinkrodt Baker MSDS, 2006 Dichloroacetic acid Irritating to the sk in Irritating to the eye IPCS/ICSC, 2000

Trichloroacetic acid Mild to moderate skin irritation Mild to moderate eye irritation OECD/SIDS ñ Trichloroacetic acid Dibromoacetic acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Tribromoacetic acid Irritating to the skin Irritating to the eye Fisher Scientific MSDS

Bromate Irritating to the skin Irritating to the eye HSDB, 2008

4.2.3 Repeated-dose toxicity

Table 4.2.3-1 lists repeated-dose toxicity studies for the chemi cals. These studies generally consider subchronic exposures, t ypically over a period of 90 days . For many of the chemicals, the target organs were the liver and kidney. This table lists the No Observed Adverse Effects Levels (NOAELs) when available.

Table 4.2.3-1: Repeated-dose toxicity studies

Chemical Exposure Route Species Value Range Reference/Comments

Hypochlorous acid a. Oral, 90-day, drinking water a. Rat a. NOAEL, 10 mg/kg-day IPCS, 2000

b. Oral, 90-day, drinking water b. Mice b. Spleen/liver weights depressed in males, but not females at the higher doses, no NOAEL identified Chloramine a. Oral, 90-day, drinking water a. Rats a. NOAEL, 5.8 mg/kg-day IPCS, 2000

b. Oral, 90-day, drinking water b. Mice b. NOAEL, 8.6 mg/kg-day Hypobromous acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine No data available; this compound is thought to be similar in toxicity to chlorinated analogue.MEPC 59/2/11 ANNEX Page 29

I:\MEPC\59\2-11.doc Chemical Exposure Route Species Value Range Reference/Comments

Chloroform a. Gavage, 90 days, doses up to 270 mg/kg-day a. Mice a. Increased liver weight IPCS, 2004

b. Oral, 7.5 years b. Beagle dogs b. LOAEL, 15 mg/kg body weight per dayDibromochloromethane a. Gavage, 13 weeks a. Rats and mice a. NOAEL, 30 mg/kg-day IPCS, 2000

b. Gavage, 90 days b. Rats b. Kidney damage at 50 and 100 mg/kg-day Bromoform a. Gavage, 13 weeks a. Rats and mice a. NOAEL, 25 mg/kg-day in rats, and 100 mg/kg-day in mice IPCS, 2000

Dichloroacetic acid a. Oral, 90 days, doses up to 72 mg/kg-day a. Dogs a. Liver weightsincreased in a dosedependant manner starting with the lowest dose. IPCS, 2000

b. Oral, 30 days b. Mice b. LOAEL is 70-100 mg/kg-day. c. Oral, 3 months c. Rats c. LOAEL is 125 mg/kg-day. Trichloroacetic acid a. Oral, 90 days, doses up to 355 mg/kg-day a. Rats a. Decrease in body weight at the highest dose IPCS, 2000

b. Oral, 90 days, dose of 785 mg/kg-day b. Rats b. Minimal evidence of liver toxicity

Dibromoacetic acid Oral, 3 week Mice Changes in liver weight at 8,400 mg/kg-day SIRI MSDS Index

Tribromoacetic acid Bromate Oral, 13 weeks, doses up to 4,000 mg/L Rats Liver toxicity at higher doses IPCS, 2000

4.2.4 Chronic mammalian toxicity

The results of chronic mammalian toxicity stud ies are listed in Table 4.2.4-1. The studies are conducted in rodents over a period of 2 years. Some of the ch emicals report liver and kidney effects, similar to the subchronic studies. Some of the chemicals show an increase in specific tumours, usually in one species. Where effects concentrations are provide d, they are higher than concentrations typically found in treated ballast water.MEPC 59/2/11 ANNEX Page 30

I:\MEPC\59\2-11.doc Table 4.2.4-1: Chronic Mammalian Toxicity Studies

Chemical Exposure Route Species Value Range Reference/Comments

Hypochlorous acid Oral, 2-year, drinking water Mice and
rats No neoplastic lesions observed. Dilatation of renal tubules in male mice receiving 275 mg/litre for more than 66 weeks. IPCS, 2000

Chloramine Oral, 2-year, drinking water Mice and
rats Increase in leukaemia observed, however this increase was not considered to be treatment-related IPCS, 2000

Hypobromous acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Chloroform Oral and gavage, 2-year Mice and
rats Liver effects noted, including tumours IPCS, 2004

Dibromochloromethane Gavage, 2-year Mice and
rats Kidney and liver effects noted at all doses IPCS, 2000

Bromoform Gavage, 2-year, doses up to 200 mg/kg-day Mice and
rats Liver effects noted at high doses IPCS, 2000

Dichloroacetic acid Oral, 2-year, doses up to 2g/L Mice and
rats Dose dependant incidence of liver tumours IPCS, 2000

Trichloroacetic acid Oral, 2-year, doses up to 5g/L Mice and
rats Dose dependant increase in liver tumours in mice, but not in rats IPCS, 2000

Dibromoacetic acid Oral, 2-year Mice and
rats Increased liver cancer in male rats California EPA, 2008

Tribromoacetic acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromate Oral, 2-year, dose of 500 mg/L Rats Liver effects IPCS, 2000

4.2.5 Developmental and reproductive toxicity

Table 4.2.5-1 lists the results of developmental and reproductive toxicity studies in rodents. For many of the chemicals, there were no effects noted on fertility or health of the fetus, even at the relatively high doses used in the studies.MEPC 59/2/11 ANNEX Page 31

I:\MEPC\59\2-11.doc Table 4.2.5-1: Developmental and reproductive toxicity

Chemical Exposure Route Species Effects Reference/Comments

Hypochlorous acid Oral, chlorinated water at 10 mg/kg-day for 7 generations Rats No effects on fertility, growth or survival IPCS, 2000

Chloramine a. Oral, concentrations up to 100 mg/L fed during breeding and gestation a. Rats a. No effects on fertility or health of offspring IPCS, 2000

b. Gavage, doses up to 10 mg/kg of body weight b. Rats b. No effects on fertility or health of offspring Hypobromous acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Chloroform Gavage, doses up to 41 mg/kg-day Mice No effect on fertility or fetal development IPCS, 2004

Dibromochloromethane Oral, 2-generation study with doses up
to 685 m g/kg-day Mice Decrease in fertility in the high-dose groups. No lethal or teratogenic effects. IPCS, 2000

Bro m ofo r m a. Gavage, doses up
to 200 m g/kg on gestation days 6-15 a. Rats a. Fetotoxic response, but no malformations. IPCS, 2000

b. Gavage, doses up
to 200 m g/kg for 105 days b. Mice b. No effect on fertility or offspring. Dichloroacetic acid a. Gavage, doses up
to 125 m g/kg-day a. Rats a. Dose-dependent effect on male reproductive function IPCS, 2000

b. Gavage, days 6-15 of gestation b. Rats b. Soft tissue abnormalities in fetal rats at doses above 140 mg/kg-day Trichloroacetic acid Gavage, days 6-15 of gestation, doses up
to 1,800 m g/kg-day Rats Body weight reduction and soft tissue malformation at higher doses IPCS, 2000

Dibromoacetic acid Gavage, doses up to 250 m g/kg-day Rats Effects on male fertility IPCS, 2000MEPC 59/2/11 ANNEX Page 32

I:\MEPC\59\2-11.doc Chemical Exposure Route Species Effects Reference/Comments

Tribromoacetic acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromate Oral, doses up to 250 mg/L Rats NOAEL of 80 mg/L HSDB, 2008

4.2.6 Carcinogenicity

Table 4.2.6-1 notes the carcinogenic classification for the chemical s by the International Agency for Research on Cancer (IARC). A few of the chemicals were not classified (hypobromous acid, bromamine, dibromoacetic acid and tribromoacetic acid) by IARC, and there is no information in the literature suggesting that they should be classified as potentia lly carcinogenic. Most of the chemicals are listed in IARC Group 3 ñ not classi fiable as to carcinogenicity in humans. For most of these chemicals, there was inadequate evidence for cancer in humans and inadequate evidence in experimental animals. Chlororofo rm and bromate are the only chemicals that are classified in IARC Group 2 B ( possibly carcinogenic to humans).

Table 4.2.6-1: Carcinogenicity

Chemical Carcinogen Classification Description Reference/Comments

Hypochlorous acid IARC Group 3 ñ not classifiable as to carcinogenicity to humans No data available from studies in humans and inadequate evidence in experimental animals. IPCS, 2000

Chloramine IARC Group 3 ñ not classifiable as to carcinogenicity to humans Inadequate evidence in humans and inadequate evidence in experimental animals. IARC, 2004

Hypobromous acid Not classified No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine Not classified No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Chloroform IARC Group 2B ñ possibly carcinogenic to humans Inadequate evidence in humans and sufficient evidence in experimental animals. IARC, 1999

Dibromochloromethane IARC Group 3 ñ not classifiable as to carcinogenicity to humans Inadequate evidence in humans and limited evidence in experimental animals. IPCS, 2000

Bromoform IARC Group 3 ñ not classifiable as to carcinogenicity to humans Inadequate evidence in humans and limited evidence in experimental animals. IPCS, 2000MEPC 59/2/11 ANNEX Page 33

I:\MEPC\59\2-11.doc Chemical Carcinogen Classification Description Reference/Comments

Dichloroacetic acid IARC Group 3 ñ not classifiable as to carcinogenicity to humans Inadequate evidence in humans and limited evidence in experimental animals. IPCS, 2000

Trichloroacetic acid IARC Group 3 ñ not classifiable as to carcinogenicity to humans Inadequate evidence in humans and limited evidence in experimental animals. IPCS, 2000

Dibromoacetic acid Not classified No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Tribromoacetic acid Not classified No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromate IARC Group 2B ñ possibly carcinogenic to humans Inadequate evidence in humans and sufficient evidence in experimental animals. IPCS, 2000

4.2.7 Mutagenicity and genotoxicity

Table 4.2.7-1 summarizes the results of various mutagenicity and genotoxicity assays. The reference documents provide detail s on the specific tests carried ou t, and the results of each of these tests. A wide range of resu lts was observed for the different ch emicals, and the different tests.

Table 4.2.7-1: Mutagenicity/genotoxicity

Chemical Study Results Reference/Comments Hypochlorous acid Several studies have shown that sodium hypochlorite produces mutagenic responses in bacterial systems and mammalian cells in vitro. However, there is no evidence of activity in mammalian test systems in vivo. IPCS, 2000

Chloramine Positive mutagenic results were observed in several bacterial in vitro assays. However, in vivo assays did not show positive results. IPCS, 2000

Hypobromous acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Chloroform Negative mutagenicity results in several in vitro and in vivo assays. IPCS, 2000

Dibromochloromethane Positive mutagenicity results in several in vitro and in vivo assays. IPCS, 2000MEPC 59/2/11 ANNEX Page 34

I:\MEPC\59\2-11.doc Chemical Study Results Reference/Comments Bromoform Positive mutagenicity results in several in vitro and in vivo assays. IPCS, 2000

Dichloroacetic acid Wide range of in vitro and in vivo tests conducted ñ mainly negative results observed. IPCS, 2000

Trichloroacetic acid Wide range of in vitro and in vivo tests conducted ñ mainly negative results observed. Some positive results were observed at high concentrations IPCS, 2000

Dibromoacetic acid Positive with and without metabolic activation in the Ames assay IPCS, 2000

Tribromoacetic acid Positive with metabolic activation in the Ames
assay IPCS, 2000

Bromate Weakly mutagenic in Ames assay with metabolic activation, caused chromosomal aberrations in Chinese hamster cell lines at high concentrations. IPCS, 2000

4.2.8 Toxicokinetics

Table 4.2.8-1 summarizes availabl e information on uptake, absorption and excretion of the chemical. Most of the chemicals are excreted in the ur ine over the course of several hours, indicating relatively short half-lives in the human body. Chloramine and trichloroacetic acid appeared to have the longest half-lives. Some of the chem icals metabolize into breakdown products, such as trichloroacetic acid and dichloroacetic acid, wh ich are also rapidly eliminated from the body.

Table 4.2.8-1 : Toxicokinetics

Chemical Study Results Reference/Comments Hypochlorous acid Hypochlorous acid metabolizes in the gut to various breakdown products, including trichloroacetic acid, a nd dichloroacetic acid HSDB, 2008

Chloramine 36 Cl-Labelled chloramine is readily absorbed after oral administrati on to rats. About 25% of the administered radioactivity is excreted in the urine over 120 h. IARC, 2004

Hypobromous acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromamine No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Chloroform A dermal study showed that more than 95% of the absorbed dose was excreted via the lungs (88% as carbon dioxide), and maximum pulmonary excretion occurred between 15 min and 2 h after dosing. IPCS, 2000

Dibromochloromethane Oral dosing in rats and mice showed that less than 2% of the dose was excreted in the urine in both species. Half-lives of DBCM in rats and mice were estimated to be 1.2 h and 2.5 h, respectively. IPCS, 2000MEPC 59/2/11 ANNEX Page 35

I:\MEPC\59\2-11.doc Chemical Study Results Reference/Comments Bromoform Recoveries of 14C -label 8 h after gavage dosing were 79% in rats and 62% in mice. The estimated half-life of bromoform was 0.8 h in rats and 8 h in mice. IPCS, 2000

Dichloroacetic acid Studies in human volunteers indicated a mean half-life in th e body of 31 minutes. IPCS, 2000

Trichloroacetic acid Readily absorbed from the gastrointestinal tract in experimental animals and humans. The half-life in the blood is 5.8 h in mice, 9.3 h in rats, 50 h in hu mans and 200 h in dogs. IPCS, 2000

Dibromoacetic acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Tribromoacetic acid No data available; this compound is thought to be similar in toxicity to chlorinated analogue. Bromate Mainly eliminated in urine. IPCS, 2000

For some of the brominated compounds (hypobromous acid, bromamine, dibromoacetic acid and tribromoacetic acid), no toxicology data could be located. It is generally assumed that brominated compounds have similar toxicologica l properties to their chlorinated analogues.

4.3 Data on environmental fate and effect under aerobic and anaerobic conditions (G9: 4.2.1.3)

4.3.1 Modes of Degradation ( b iotic and a biotic)

Aerobic degradation : TRO, hypochlorous acid and hypobromous acid decay in seconds to hours as discussed in section 7.2.2 and in Heltz (1981), thus, little or no aerobic degradation is expected. Biodegradation of the Relevant Chemicals in presented in Table 4.3.1-1.

Table 4.3.1-1: Aerobic degrada tion for Relevant Chemicals

Chemical Aerobic Degradation Reference THM - Chloroform Results range from no degradation in 25 weeks up to 100% degradation in 28 days; The 28-d results occurred primarily because of volatilization Howard (1993)

THM -Dibromochloromethane 25-39% loss in 28 days; static flask Howard (1992) THM -Bromoform 35-48% in 28 days when incubated with sewage seed Howard (1993)

HAA -Dichloroacetic acid 83-95% lo ss in 20 to 30-d BOD tests; 97% loss in 14 days using sludge inoculum TOXNET (2008)

HAA -Trichloroacetic acid 7% loss of 100 mg/L compound in a 28-day BOD test TOXNET (2008)

HAA -Dibromoacetic acid No data found HAA -Tribromoacetic acid Bromate No data foundMEPC 59/2/11 ANNEX Page 36

I:\MEPC\59\2-11.doc Anaerobic degradation : TRO, hypochlorous acid and hypobromous acid decay in seconds to hours as discussed in section 7.2.2 and in Heltz( 1981), thus, little or no anaerobic degradation is expected. Biodegradation of the Relevant Chemicals in presented in Table 4.3.1-2.

Table 4.3.1-2: Anaerobic degrada tion for Relevant Chemicals

Chemical Anaerobic Reference THM ñ Chloroform Slow degradation Howard (1990) THM ñBromodichloromethane 100% loss in 2 weeks; mixed methanogenic bacterial culture Howard (1990)

THM ñDibromochloromethane 100% loss in 2 weeks; mixed methanogenic bacterial culture Howard (1990)

THM ñBromoform >99% loss in 2 days in biofilm column; mixed methanogenic bacterial culture Howard (1990)

HAA ñDichloroacetic acid No data found HAA ñTrichloroacetic acid No data found HAA ñMonobromoacetic acid No data found HAA ñDibromoacetic acid No data found HAA ñTribromoacetic acid No data found Bromate No data found

4.3.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient

The octanol/water partition coeffi cients (Pows) and bioaccumul ation factors (BCFs) for the Active Substances and Relevant Chemicals ar e given above in section 4.1.5. The adsorption coefficients (Kocs) for the Active and Rele vant Chemicals are gi ven in section 4.1.4.

4.3.3 Persistence and identification of the main metabolites in the relevant media

It is well documented that FAC will react in fr eshwater to form a number of chloro-organic compounds, oxidation products, and chloride. Likewise , it is well documented that chlorine will react with Br- in saltwater to fo rm free bromine which reacts with nitrogen to form bromamines which in turn form a number of bromo-organi c, oxidation products, and Br-. The Relevant Chemicals listed in the above tables are the by-products expect ed from the chlorination of freshwater and saltwater ballast . The persistence of the above by-products is given in sections 4.1.4, 4.1.5, and 4.3.1.

4.3.4 Reaction with organic matter

Several oxidant decay reactions have been iden tified. The principal types of decay reactions which can ultimately react with organic matter ar e: 1) oxidation of amino-nitrogen (breakpoint reaction) which in turn react with organic matter; 2) oxi dation of carbon; and 3) organic substitution. The most important decay reac tions are probably those associated with the oxidation of amino-nitrogen which are important in the breakpoint phenome na of the chlorineammonia system. The breakpoint reactions are a function of chlorine dose, amino-nitrogen concentration, pH, temperature, and time of reaction.

Trihalomethanes are unquestionabl y ubiquitous products of chlorina tion. Several variables can affect THM yields which include pH, temperature, chlorine dose, total organic carbon, and type of chlorine residual. Other f actors being equal, higher pH tend s to produce higher levels of THM after a given contact time. Higher temperatures accelerate the rate of THM appearance; however,MEPC 59/2/11 ANNEX Page 37

I:\MEPC\59\2-11.doc it is not clear whether temperatur e affects the ultimate yield. In creasing chlorine dose increases yield up to point; however, several studies indi cate that a plateau is reached. THM yields correlate positively with total organic carbon, but th ere is a great deal of scatter. Chloramines appear to produce little or no THM.

Oxidation of carbon can play an important role in oxidant decay when natural waters containing various amounts of organic matter are chlorinated. CO 2 has been shown to be a major product of chlorination of natural estuarine water. Halocarb ons have been shown to occur to a lesser degree by carbon oxidation. The production of halocarbons by substitution reactions also constitutes a decay mechanism for chlorine. However, the lite rature indicates (Helz, G.R. 1981) that only a few percent of the chlorine in typical doses is consumed in substitu tion reactions during the decay process.

4.3.5 Potential physical effects on w ildlife and benthic habitats

No data were found that indicated the Active S ubstances and Relevant Chemicals could cause potential physical effects to wildlife.

4.3.6 Potential residues in seafood

Based on the log Pows and BCFs of the Active Substances and Relevant Chemicals, it is unlikely that significant residues will accumulate in tissues which in turn could impact the consumption of seafood. No data were found that suggest that the Active Substances and Relevant Chemicals impart a foreign flavour or odour in the organisms exposed to the chemicals.

4.3.7 Any known interactive effects

No interactive effects of the Relevant Chemicals with fresh and salt ballast water have been identified

. 4.4 Physical and chemical properties of th e Active Substances, Relevant Chemicals and treated ballast water (G9: 4.2.1.4)

Available physical and chemical properties of the Active Substances ìAs Generatedî (300 to 1

, 500 mg/l TRO as HOCl) and ìAs Appliedî (0 ñ 6 mg/l TRO as a mix of HOBr, HOCl and haloamines) into the ballast water at a maximum level of 6 mg/l (dose level) and a minimum level of less than 0.1 mg/l (disch arge level), and treated water are presented in Table 4.4-1.

Table 4.4-1: Physical and chemical propert ies of Active Substances and Treated Water

Properties Active Substance: As Generated HOCl: 300 ñ 1,500 mg/l Active Substance: As Applied TRO: 0 ñ 6 mg/l Treated Ballast Water

TRO ≤ 0.1 Appearance and Odour Colorless to light yellow-green liquid with chlorine-like odour Colorless liquid with light chlorine-like or no odour Same as untreated water

Vapour Pressure Same as ballast water Same as ballast water Same as untreated water Boiling Point Same as ballast water Same as ballast water Same as untreated water Specific Gravity Same as ballast water Same as ballast water Same as untreated water Volatile Percentage Not determined Not determinedMEPC 59/2/11 ANNEX Page 38

I:\MEPC\59\2-11.doc Properties Active Substance: As Generated HOCl: 300 ñ 1,500 mg/l Active Substance: As Applied TRO: 0 ñ 6 mg/l Treated Ballast Water

TRO ≤ 0.1 Flash Point/method UEL/LEL Vapour Density (Air=1): Not determined Not determined Same as untreated water

Melting Point Not determined Same as ballast water Same as untreated water Solubility in Water 100% 100% pH 8.0 ñ 8.5 Same as ballast water Same as untreated water Auto Ignition Temperature Dissociation Constant (pKa) HOCl - 7.5 HOCl - 7.5 HOBr - 8.5 Redox potential, mV 300 - 800 200 ñ 400 Corrosivity to material of equipment Corrosive Corrosive Same as untreated water

Viscosity @20°C) Same as ballast water Same as ballast water Same as untreated water Surface tension Same as ballast water Same as ballast water Same as untreated water

Note : Shaded area = Not Applicable

There was no information available for physical and chemical properties of the Relevant Chemicals in treated seawater at concen tration levels iden tified in section 3.2.

The Material Safety Data Sheets for the chemicals identified as Relevant Chemicals in section 3.2 are presented in Appendix A (refer to confidentia l part of the application) for commercially available forms of these chemicals, as a point of reference only. The list of identified commercially available chemicals is presented in Table 4.4-2.

Table 4.4-2: Commercially Av ailable Relevant Chemicals

RC Commercially available form CAS Number Source Trichloromethane Liquid, 100% Wt. 67-66-3 www.ScienceLab.com Tribromomethane Liquid, 100% Wt. 75-25-2 www.ScienceLab.com Dibromochloromethane Liquid, 98% Wt. 124-48-1 www.Sigma-Aldrich.com Trichloroacetic acid Crystals, 100% Wt. 76-03-9 www.ScienceLab.com Tribromoacetic Acid Crystals, 99% Wt. 75-96-7 www.Sigma-Aldrich.com Dibromoacetic acid Crystals, 97% Wt. 631-64-1 www.Sigma-Aldrich.com Dichloroacetic acid Liquid, 100% Wt. 79-43-6 www.ScienceLab.com Sodium bromate Crystals, 100% Wt. 7789-38-0 www.ScienceLab.com

4.5 A nalytical methods at environ m e n tally relevant concentrations

To date, Siemens has used tw o accredited environmental labor atories for all environmental analytical services:

- Enviroscan Analyticalô Services, Rothschild, WI, United States; and - Underwriters Laboratories (UL), South Bend, in the United States.MEPC 59/2/11 ANNEX Page 39

I:\MEPC\59\2-11.doc Enviroscan was responsible for analysis of THMs and TOC and UL was responsible for analysis of HAAs and sodium bromate.

All chlorine analysis was perfor med internally either by Siemens personnel or subcontractors, such as NIOZ, trained by qualified Siemens ch emists, using HACH spectrophotometer and the HACH reagent kits.

The relevant analytical methods used for all Active Substanc es and Relevant Chemicals are listed in Table 4.5-1 and provided in the Appendix B. Appendix B also provid es standard operating procedures used by Enviroscan and UL.

Table 4.5-1: Analytical Methods

Chemical/ Parameter USEPA Method Description Method Reporting Limit* TOC 415.1 Combustion 0.5 mg/l TRO/FAH 330.5 DPD-calorimetric method 0 mg/l THMs 524.2 Capillary column gas chromatography/ mass spectrometry Trichloromethane 0.4 μg/l Tribromomethane 0.2 μg/l BromoDichloromethane 0.4 μg/l Dibromochloromethane 0.2 μg/l HAAs 552.2 Liquid extraction, derivatization and gas chromatography with electron capture detection Trichloroacetic acid 1.0 μg/l Tribromoacetic Acid 4.0 μg/l Dibromoacetic acid 1.0 μg/l Dichloroacetic acid 1.0 μg/l Monochloroacetic acid 2.0 μg/l Monobromoacetic acid 1.0 μg/l Sodium Bromate 317.0 Ion chromatography with the addition of a postcolumn reagent for trace bromate analysis 1.0 μg/l

* The indicated method report limits were demonstrated to be achievable, but depend on a sample matrix.

5 U SE OF THE ACTIVE SUBSTANCE (G9: 4.2.6)

5.1 Manner of Applicatio n and Dosage

The SiCURE system will treat ballast water on intake.

SiCUREô BWMS is not based on a fixed Active S ubstance dose; it is ba sed on variable dosing necessary to achieve a certain oxidizing power of the treated water - its ORP potential. The tests conducted in the laboratory sett ings using seawater from the North Sea off the Texel Island, the Netherlands show that this can be achieve d with an HOCl dose not exceeding 6 mg/l, most likely within 2 to 6 mg/l range. The land-based and shipboard tes ting programme will show if the maximum concentration of 6 mg/l can be lowe red and the output of the SiCUREô BWMS will be adjusted accordingly. It is expected that the dose level may be less than the one determined in the laboratory testing due to hi gher efficiency of the commercia l size 40 micron weave screen filter in retention phytopl ankton compared to the 50 micron nylon mesh used in the bench-top tests.MEPC 59/2/11 ANNEX Page 40

I:\MEPC\59\2-11.doc Dosing of the Active Substance as discussed in section 5.2 will be split about 10 to 1 between the disinfection and biofouling control injection streams using preset fl ow control valves. Therefore, a typical dose range for disinfection will be be tween 2.0 and 5.5 mg/l, while a typical dose range for filterís biofouling contro l will be at 0.2 to 0.5 mg/l.

Required chlorine dosing will be determined based on an OR P reading and controlled by PLC to reduce or increase DC current drawn from the transformer-rectifier to the electrochemical generator as necessary.

5.2 O perational overvie w and process description

Patent pending SiCUREô BWM system us es three major system components:

- a high efficiency, self-flushing filter to remove all of zooplankton and a part of phytoplankton;

- an electrochemical generato r that in-situ produ ces hypochlorous acid from seawater to provide disinfection of the filtered ballast water; and

- an ORP control that regulates hypochlorous ac id dose to meet biocide demand of the water being treated.

Tests conducted by Siemens with cooperation fr om NIOZ have shown that a 50 micron filter could provide a complete removal of zooplankt on. Removal of zoopla nkton is essential to reducing chlorine dose levels required for disinf ection of the ballast water, thus minimizing potential risks of corrosion a nd generation of disinfection by -products. The SiCUREô BWMS utilizes a 40 micron filter that was proven to be far more effective than a 50 micron filter in removing not just zooplankton, but a significant fraction of phytoplan kton. This is expected to provide an additional reduction in the required biocide dose as opposed to ones observed in the laboratory setting.

Hypochlorous acid is produced in-situ in th e electrochemical generator by using a 5.5 m 3 /h (small capacity systems) or 11 m 3 /h (large capacity systems) side stream taken from the ballast water. It is cleared of the entrained by-product hydrogen gas that is safely vented overboard, and immediately injected into the ballast water. While the flow of the side stream is maintained constant, the biocide concentration in this flow is varied by the dire ct (DC) current drawn through the electrochemical cell. Siemensí proprietary CHLOROPAC Æ technology is used to generate HOCl.

CHLOROPAC Æ is well known in the maritime industry as it has been used for biofouling control of the main engine and auxiliary cooling wa ter for over 30 years, with over 2,000 commercial and navy shipboard installations wo rldwide. It is known for its re liability and low maintenance. The main feature of this generator is that it does not require removal of the scale that typically forms on the cathodes in the elec trochemical produced by other manuf acturers. It also employs Siemens proprietary anode coatin gs that allow producing HOCl in a wide range of seawater temperatures and salinities. Th ere is no bulk storage of produced HOCl, it is injected into the ballast water main as soon as hydrogen gas had b een removed. In case a degas tank is used to remove hydrogen, there will be very small amount of HOCL solution present in the tank. Depending on a size of the SiCUREô system, HOC l solution is produced with a strength of 0.01 to 0.15 % Wt.MEPC 59/2/11 ANNEX Page 41

I:\MEPC\59\2-11.doc If CHLOROPAC Æ is the heart of the SiCUREô BWMS, ORP control is its brain. Widely used in controlling disinfection of th e recreational and cooling water, it is an ultimate and, importantly, low maintenance, analytical instrume nt measuring oxidizing power of water treated with HOCl or HOBr and practica lly invariant of the water conditions such as pH, salinity, temperature and, most importantly, its pollution level. Siemens had been working on ORP control for biofouling control of shipboard applications since 2003 and gained valuable expertise in this area that was invaluable in implementing its ORP control logic for ballast water treatment. A typical SiCUREô BWM system is provided in the Figure 5.2-3.

Figure 5.2-3: Typical SiCUREô BWMS Skid

SiCUREô systemís ORP based control logic allows using variable, on-demand biocide dosing to reach an oxidizing strength of the treated water ne cessary to achieve a proper level of disinfection.

The SiCUREô system is designed for shipboard applications for both ne w builds and retrofits. The system can be supplied as a skid mount or co ntainerized, fully integrat ed package or as loose components.

There will be no dry dock requirem ent for the system installation for most of the retrofits. Those vessels that have submersible ballast water pump will require dry dock for installation of the SiCUREô BWMS.

5.3 R etention time

The tests show that employment of a 50 micron f ilter and an ORP controlled biocide treatment provides conditions when di sinfection of the ballast water can be achieved within the very first day of treatment, most likely within a few hours. However, the retention tim e of the ballast water treated with SiCUREô BWMS has to be defined based on the Active Substance residual in the treated water prior to its discharge into the envi ronment. While this could be remedied by using a dechlorination step prior to the discharge, Si CUREô project team woul d like to avoid having any chemicals on board as this would present sh ip crew with unnecessary hazards related to the chemicalsí handling and maintenance.MEPC 59/2/11 ANNEX Page 42

I:\MEPC\59\2-11.doc The tests conducted to date show that 5 days after the treatment , the Active Substance level is expected to be about 0.1 mg/l or less. At this poi nt, at least till the land-based tests are completed, the retention time will stand at 5 days.

Future tests will show if Active Substance residua ls could be achieved at the environmentally safe levels in a shorter retention ti me, preferably within 1 to 3 days.

5.4 System monitoring and control, crew interaction
The SiCUREô BWM system is controlled by a Siemens PLC, programmed to initiate operation when all the system permissives are satisfied . A Human-Machine Inte rface (HMI) is also provided which includes archiving capability. SiCUREô PLC will be linked. The system is designed to provide a safe mode of operation with a minimum involvement from the crew.

The SiCUREô BWM system includes all necessary instrumentation and controls. A System Control Panel includes PLC and all controls accessories for proper operation of the system. A communication module is included to connect to the shipís bridge and relay process information. Also available to the bridge are start, stop and the emergency shutdown of the electrochlorination unit. SiCUREô BWM system operation is linked to the star t and stop of the balla st water operation. The instruments and control devices provided to monitor the process are listed in Table 5.4-1

. Table 5.4-1: Monitoring and control devices

Device Purpose Monitoring Devices Differential Pressure Switch for the Filter Measure the pressure drop in the filtering basket. The unit will backwash automatically when a preset pressure differential is reached or is activated by a timer with preset flushing intervals. Flow Instrument for the filter backwash outlet Measure the backwash flow

Flow Instrument at generator inlet Measures flow of ballast water side -stream flow to the electrolyzer

Differential Pressure Switch for the generator Indicate any clogging of the chlorination cells.

Leak detector for the generator Monitor any leak in the generator cells.

Pressure Instrument at Air Blower Discharge Monitors air pressure when the blower is started. A low pressure indication will alarm and shut down the system. Flow Instrument at Degas Tank Vent Monitors air flow through the dega s tank. A low flow indication will alarm and shutdown the system Level Instrument for Degas Tank Monitor the hypochlorite solution level in the tank when the system is in operation. High and low level al arms are programmed for indication. At high level alarm the transformer rectifier and the inlet flow to the degassing tank are stopped. The hypochlorite dosing pump will continue to operate to bring down the level be fore shutting down. At low level the hypochlorite dosing pump will shut down. Flow Instrument for filter fouling control Measures flow of Active Substances upstream the filter

ORP Instrument Monitors ORP readi ng in the treated ballast water. Control Devices Failsafe Electronic and Pneumatic Valves Segregates SiCUREô BWMS from the shipís ballast water system in case of emergency such as a fire or a power loss.MEPC 59/2/11 ANNEX Page 43

I:\MEPC\59\2-11.doc SiCUREô BWMS will have a data acquisition system . PLC will collect and transmit to the data acquisition system those parameters that are vital for the reliable performance of the filtration and disinfection subsystems. The parameters will in clude differential pressure setpoint (backwash trigger), differential pressure an d backwash duration for the filter and ORP setpoint, ORP value, DC current, DC voltage, electrochemical generato r flow, differential pre ssure in the hydrogen degas tank ñ for the disinfection system.

Operation of the SiCUREô system is provided in a fully automated mode and requires minimum maintenance limited to:

- inspect all SiCUREô equipment prior to op eration and after ballasting is completed;

- tighten any loose item in the system;

- perform visual checks of the system in operation. Maintain system tidiness and ensure equipment is operating properly. Log any observation;

- check the ORP monitor as appropriate . Log extreme changes in reading;

- check the system data logge r and examine the data record ed. Look for any variation; and

- monitor any abnormal alarm.

5.5 System re q uirements

Utility Requirements : The system requires 380-480 V, 3-pha se 50/60 Hz AC power input, air (for failsafe valves) and small amou nt of fresh water for a filter rinse (about 150 L per treatment).

Space Requirements : The footprint of the system will depend on a size and configuration of the system. The SiCUREô BWM system can be provide d as skid-mounted, fully enclosed in a 20-ft container or as loose components and installed e ither in an engine room, pump room or on a deck. A typical footprint of the skid-m ount SiCUREô system to treat up to 1000 m 3 /h will require about 4.2 m 2 . Additional footpr int is required for a filter. Its size wi ll depend on a horizontal or vertical arra ngement of the filter. Fo r example, for up to 350 m 3 /h ballast water flow, filterís footprint will be of 1.55 m 2 for a vertical arrangement or 3.6 m 2 for a horizontal arrangement.

Personnel Require m ents : The SiCUREô BWMS i s designed to work in a fully auto m atic mode ñ there is no special pers onnel requirements for operating th e system, rather then some limited preventive maintenance measure described be low. It is expected that the preventive maintenance measures will be limited to less than 2 hours per year to verify ORP probe reading and replace the probe, if necessary once every 6 to 12 months. If required, ship crew can start and stop the SiCUREô system manually.

Siemens worldwide network of t echnical service and support specia lists will ensure that a proper training and preventive maintena nce are provided during regular po rt calls by a ship carrying SiCUREô system.MEPC 59/2/11 ANNEX Page 44

I:\MEPC\59\2-11.doc 5.6 System reliability

The SiCUREô BWMS is based on technology modules that have been in use in maritime, oil and gas, power and chemical industries for over 35 years. More than 2000 Siemens Shipboard Chloropac Æ systems have been provided to major ope rators such as Bergesen, BP, Carnival, Leif Hoegh, Matson, Shell, Exxon Mobil, Statoil, Qatar Gas and Chevron.

Many of those installations operating around the cl ock have not required any maintenance for as long as 12 years.

The SiCUREô BWMS reliability is ensured by the manufacturing and quality practices adopted by Siemens. Siemens divisions providing solution s to maritime industry are vertically integrated; the key components of the system such as el ectrodes and anode coati ngs are manufactured directly by Siemens.

5.7 System locations, con s iderations and limitations

System Locations and Considerations : Based on Siemens experience with Chloropac Æ shipboard appli c atio n s , it is expe c t ed that ev e r y install a ti o n will require engin e ering work together with a shipowner, ship operator and a naval architect to determine the best location and piping configuration for the SiCUREô BW MS to provide for its safe operation. A location for each installation will have to be a pproved by a Classification Society.

While electrochlorination part of the SiCUREô syst em can be installed at various locations such as in the engine or pump rooms or on a deck, it is preferred that the filter be installed near the ballast water pumps that are typi cally designed for low pressure.

Limitations : Major limitation of the SiCUREô BWMS is related to the manner the Active Substances are produced on board the ship. Si CUREô system produces Active Substance in a side-stream to a concentration of 300 to 1500 mg/l. This design was selected to eliminate any possibility of the hydrogen gas by-product from accumulating in the ballast tanks. The requirement for a relatively high co ncentration of the generated bioc ides limits application of the SiCUREô system to those ships that: meet the following criteria:

- operate only in salt or brackish water; and

- do not operate only in fresh water.

5.8 Operational safety features and alarms

The instruments and equipment setup of the SiCU REô BWMS will need to be in the ready state for the system to begin operation. Any abnormal or alarm status will be indicated in the PLC. The system is also provided with data logging to archive selected process conditions while operating. Controls include provisions to communi cate with the shipsí central controls at the bridge. When connected the SiCU REô system operation can be mon itored remotely at the bridge.

When the system is started in automatic mode the Programmabl e Logic Controller (PLC) will cycle through all the permissives before initiating equipment to operate per the programmed sequence. If any of the permissives is not read y to operate, an alarm will signal and will be logged in the alarm list. The table below list s the systemís common fa ults and the steps to resolve the condition.MEPC 59/2/11 ANNEX Page 45

I:\MEPC\59\2-11.doc Table 5.8-1: Common fault condit ions and troubleshooting guide

Fault Condition What/Where to check Probable Cause
Electrolyzer a. Suction pressure for seawater booster pump a. Seawater supply pressure low. b. Seawater filter fault, i.e. plugged (see filter operating manual) b. Seawater booster pump operation See Seawater booster pump operating manual Low inlet flow to hypochlorite generator

c. Flow control valve at inlet to generator See flow control valve operating manual

Air blower fault a. Motor operation Short circuit, contactor unlatched at Motor Control Centre a. Air blower a. Motor fault. See operating manual b. Contactor unlatched at Motor Control Centre b. Flow instrument at degassing equipment vent See flow instrument operating manual Low or no dilution air flow

c. Pressure instrument at air blower discharge See pressure instrument operating manual

a. Degassing equipment Level Instrument See level instrument operating manual

b. Hypochlorite dosing pump See hypochlorite dosing pump operating manual Degassing equipment low level fault

c. Generator inlet flow instrument See flow instrument operating manual

a. Degassing equipment level instrument See level instrument operating manual Degassing equipment high level fault b. Hypochlorite dosing pump See hypochlorite dosing pump operating manual a. Analyzer feed pump See pump operating manual Dosing Analyser fault b. ORP Analyzer instru ment See ORP analyzer operating manual Transformer/ Rectifier Fault Transformer /Rectifier alarm lights See transformer/rectifier operating manual

Automatic filter fault Automatic filter control panel See automatic filter operating manual

Filter Continuous flushing of the filter Check flow and pressure The pre ssure differential switch remains triggered due to inability to clean the screen after flushing cycle Limit Switch failure Check the limit disc located on the drive shaft if moved or not located properly. The PLC is programmed to allow maximum travelling time of the drive shaft between the limit switches for 40 seconds which after the shaft is ìfallingî out of the threaded drive mechanism to prevent damage. A fault is registered and the system stops.MEPC 59/2/11 ANNEX Page 46

I:\MEPC\59\2-11.doc The SiCUREô BWM system uses only a side stream flow from the ballast water pipe to produce an Active Substance. In the event that th e SiCUREô BWM system stops its operation, the alarm will sound, but the ballasting operation can continue without interruption and presenting risks to the ship safety.

In the event the sea water filter starts clogg ing and is required to be bypassed, raw sea water will be the supply for the SiCUREô hypochlorite generato r. Extended operation in this mode is not recommended as this will eventually result in clogging the generator cells resulting in an extensive clean-up of all the equipment before normal operati on can commence. A separate strainer and a spare strainer basket are provide d for the protection of the electrochlorination section of the system that will enable the user to finish balla sting. This electrochlorination strainer may experience frequent fouling and will need manual cleaning of the basket to keep its operation. When this happens, it will require shuttin g down the system for the time to replace the fouled strainer basket with the clean spare basket. One spare basket is available on board to keep the downtime to a minimum. Once the basket is replaced the system can commence operation. The defouled strainer basket will then be cleaned and will become the spare.

5.9 Various procedures and management measures

5.9.1 Fire

As the SiCUREô system does not require the st orage of any chemicals on board, there is no associated fire/explosion risk. The generation of sodium hypochlorite in-situ eliminates the need for chemical storage, however does result in the generation of hydroge n gas. The system includes a degas tank with air blowers and hydrogen gas detecting instrument ation to ensure that the hydrogen gas has been safely d iluted with air prior to venting.

5.9.2 Flooding

The SiCUREô system is installed such that the ships ballasting system can run independently of its operation. The connection to the ballast water piping system is made via Type Approved automatic valves and piping. In case of catastr ophic failure of any of the components of the SiCUREô system, the emergency stop would auto matically close these valves resulting in complete isolation from the ships ballast water piping.

5.9.3 Accidental release measures

The SiCUREô system has the required alarms de sign to detect any possi ble leaks of the Active Substance on a ship. Since the system does not store the chemicals on board, any possible release should be of small volume.

If spill of concentrated Active Substance occu rs, it can be absorbed with inert material (e.g., vermiculite, sand or earth), then placed in suitable container for disposal. The spills should be cleaned up immediately while wearing a ll personal protective equipment. A proper ventilation should be provided.

Concentrated Active Substance may react with certain organic compounds causing fire and with acids generating chlorine fumes. No reactive ch emicals and acids should be stored around the SiCURE BWMS.MEPC 59/2/11 ANNEX Page 47

I:\MEPC\59\2-11.doc If the spill of the treated ballast water occurs, it can be just hosed down as within an hour the concentration of the Active Substa nce in the sill will be similar to the ones that can be found in drinking water or swimming pool water.

Respiratory Protection: None required und er normal use conditions. Use NIOSH/MSHA approved organic vapour-acid-gas resp irator with filter (qualified to wear respirator) during spill clean-up or other conditions that might produce irritating ch lorine-like fumes.

Skin Protection: Wear neoprene or rubber gloves and other protective clot hing as appropriate to prevent skin contact.

Eye Protection: Safety glasses with face sh ield or chemical goggl es are recommended.

Ventilation Protection: Use local ex haust at points of vapour emission.

Other Protection: Safety showers, with quick opening valves which stay open, and eye wash fountains, or other means of washing the eyes with a gentle flow of cool to tepid tap water should be readily available in all areas where this ma terial is handled or stored. Water should be supplied through insulated and heat-traced lines to prevent freeze-ups in cold weather.

Proper training of the crew should be regularly conducted to become familiar with the required measures against the accidental releases.

5.9.4 Marine environment release

It is considered very unlikely that there will be an accidental release of the Active Substances into the marine environment. There are cu rrently no recommended meas ures to contain the release if occurred. However, as the spill should be of small volume and chlorine decays fast, the release should provide very limited impact on the environment. Any spill has to be properly reported to the authorities

. 5.9.5 Conditions for control discharge

No control discharge scenario is anticipated with the SiCUREô BWMS as there will be no chemical storage on board.

5.10 Evaluation of management measures

Management measures for dealing with the emer gency situations are limited to an adequate training by the ship management and Siemens pers onnel. The measures described in section 5.8 are considered to be adequate to properl y operate and m anage the SiCUREô B W M s yste m

.

6 HAZARD CLASSIFICATION AND MATERIAL SAFETY DATA SHEETS (G9: 4.2.7)

Hazard identification for Active Substances and Re levant Chemicals provided in Table 6-1 below is based on MSDS of commercia lly available products that cont ain referenced chemicals at significantly greater con centrations that produced by the Si CURE BWMS or could be found in the treated ballast water. Theref ore the hazard identification pres ented in the Table 6-1 reflects potential hazards only and does not indicate any potential for e xposure. All referenced MSDS are provided in Appendix A.MEPC 59/2/11 ANNEX Page 48

I:\MEPC\59\2-11.doc Table 6-1: Hazard identification for Ac tive Substances and Relevant Chemicals

Chemical Name CAS Number AS, RC, BP DSCL (EEC) Hazard Identification: R-Phrases & S-Phrases Hypochlorous acid (as 5% NaOCl solution) 7681-52-9 AS R8, R31, R36/38 S28, S36/37/39, S45 Hypobromous acid (as 1.72% Wt. Bromine water) 7726-95-6 AS R36/38

Hydrogen Gas 1333-74-0 BP F+: R12 S9, S16, S33 Trihalomethanes Trichloromethane, 100% Wt. 67-66-3 RC R20/22, R38, R40 S36/37 Dibromochloromethane 98% Wt. 124-48-1 RC R22 Tribromomethane, 100% Wt. 75-25-2 RC R22, R36/38, R40 Haloacetic acids Dichloroacetic acid, 100% Wt. 79-43-6 RC R21, R35 Trichloroacetic acid, 100% Wt. 76-03-9 RC R35, R50/53, S26, S36/37/39, S45, S60, S61. Dibromoacetic acid, 97% Wt. 631-64-1 RC C R20/21/22-34 S26-36/37/39-45 Tribromoacetic acid, 99% Wt. 75-96-7 RC C R35 S: 26-36/37/39-45 Sodium Bromate, 100% Wt. 7789-38-0 RC R38, R41

7 RISK CHARACTERIZATION

7.1 Screening for persistence, bioaccu mulation, and toxicity (G9: 5.1)

7.1.1 Persistence (G9: 5.1.1.1)

The Active Substances (TRO, hypochlorous and hypobr omous acids) are not persistent. All of the Relevant Chemicals are persistent using Proce dure (G9) criteria of a half-life >60 days in marine water or >40 days in freshwater. Th e data are summarized below in section 7.1.4 as required by Procedure (G9) (IMO, 2008a).

7.1.2 Bioaccumulation (G9: 5.1.1.2)

None of the Active Substances or Relevant Chemicals are expe cted to bioaccumulate using Procedure (G9) criteria of a log Pow <3. The data are summarized below in section 7.1.4 as required by Procedure (G9) (IMO, 2008a).

7.1.3 Toxicity tests (G9: 5.1.1.3)

The chronic toxicity database in this dossier (Table 4.1.2-1) indicates that none of the Active Substances appear to be toxi c to fish (0.04 mg/L) and crus taceans (0.012 mg/L) based on a chronic NOEC criterion of <0.01 mg/L. The Active Substances may have the potential to beMEPC 59/2/11 ANNEX Page 49

I:\MEPC\59\2-11.doc toxic to algae based on unacceptable OECD data when the chronic NOEC criterion of <0.01 mg/L is used. Since the chronic data show n in Table 4.1.2-1 for algae did not met OECD 201 Guideline acceptability criteria but were includ ed to provide an indication only of potential toxicity, further speculation rega rding chronic toxicity of the Active Substances to algae is not warranted. No chronic toxicity data were f ound for any trophic level exposed to hypochlorous acid or hypobromous acid.

The chronic toxicity database (Table 4.1.2-1) shows for the Relevant Chemicals for which acceptable OECD chronic toxicity data are av ailable (bromate and two THMs) that these compounds are much less toxic than the Active S ubstances. For example, the bromate NOEC for algae is 8 mg/L which is almost 3 orders of magnitude above the <0.01 mg/L level set for the Active Substances. The chronic NOECs for chloro form range from a low of 1.5 mg/L for fish up to 216 mg/L for algae. A 10 mg/L NOEC for al gae exposed to bromoform is 3 orders of magnitude higher than the <0.01 mg/L level set for the Active Substa nces. No chronic data were found for dibromochloromethane. No acceptable OE CD chronic data were found for any of the four HAAs under considerat ion for this dossier.

The toxicity data are summarized below in section 7.1.4 as requir ed by Procedure (G9) (IMO, 2008a).

7.1.4 PBT criteria for Active Substance (G9: Table 1)

Table 7.1.4-1: Persistence (P), bioaccumulation (b), and toxicity (t) data for the Active Substances and Relevant Chemicals

Chemical (P) (Yes or No) (B) (Yes or No) (T) (Yes or No) Active Substances TRO No No Yes - -Fish, crustaceans, and algae Hypochlorous acid No No Yes - Fish and Crustacean Hypobromous acid No No Yes - Based on the toxicity of hypochlorous acid FAC No No Yes - Fish data that did not meet OECD Guidelines Yes - Crustaceans data that did not meet OECD Guidelines Yes - Algal using spike tests data that did not meet OECD Guidelines Relevant Chemicals THM - Chloroform Yes No No - Fish, crustaceans, and algae THM -Dibromochloromethane Yes No No - Fish THM -Bromoform Yes No No - Fish, crustaceans, and algae HAA -Dichloroacetic acid Yes No No - Crustaceans and algae HAA -Trichloroacetic acid Yes No No - Fish, crustaceans, and algae HAA -Dibromoacetic acid Yes No Reliable data not found HAA-Tribromoacetic acid Yes No Reliable data not found Bromate Yes No No - Fish, crustaceans, and algaeMEPC 59/2/11 ANNEX Page 50

I:\MEPC\59\2-11.doc 7.2 Evaluation of the treated ballast water (G9: 5.2)

7.2.1 Environmental data from the proof-of-concept tests

Siemens carried out numerous tests prior to appl ying for Basic Approval. The first goal of the testing was to test the SiCURE ô BWMS control logic and to pr ove that all aq uatic invasive species can be eliminated safely from the ballast water, prior to discharge. The second goal was to carefully evaluate the Active Substance residu als and disinfection by-products; results of this study will be presente d in this section.

Testing was carried out in collaboration with th e Royal Netherlands Institute for Sea Research (NIOZ), P.O.Box 59, NL-1790 AB Den Burg, Texel, the Netherlands, more particularly with their Department of Biological Oceanogr aphy led by Dr. Marcel J.W. Veldhuis.

As seen from Fig. 7.2.1-2 (refer to confidential part of the application), water with low chlorine demand treated with 10 or 5 mg/l of chlorine maintains its high oxidizing power of about 750
to 820 mV over the entire 5-day retention time, while free chlorine residual is within the 1 to 4 mg/l and 4 to 8 mg/l range, correspondingly. At these ORP and free chlorine le vels one may expect a high level of corrosion to the ba llast water tank and high rate of DBP generation during the entire retention period. This is a typical example of overchlorination. As seen from Fig ure 7.2.1-3 (refer to confidential part of th e application), even at high TSS concentrations of 200 mg/l, the same trend persists with the 10 mg/l fixed chlorine dose.

Table 7.2.1-1 shows results of the DBP analysis at the end of the 5-day retention time for water treated with 10 mg/l and for an ORP controlled chlorine dose.

Table 7.2.1-1: DBP profile in ìwinterî water after 5 days retention time

Fixed Chlorine Dose SiCUREô ORP controlled Sediments, mg/l 0 200 0 200 Chlorine Dose, mg/l 10 10 0.9 4.2 Total THM, μg/l 169 283 15.4 97

Trichloromethane < 0.4 3 < 0.4 < 0.4 Tribromomethane 164 268 15.4 93 Bromodichloromethane < 0.4 < 0.4 < 0.4 <0.4 Dibromochloromethane 5.5 12 < 0.2 4

Total HAA, μg/l 75.6 130.4 7.6 36

Monochloroacetic acid <2.0 2.5 <2.0 <2.0 Dichloroacetic acid <1.0 <1.0 <1.0 <1.0 Trichloroacetic acid <1.0 <1.0 <1.0 <1.0 Bromoacetic acid 5.6 7.9 <1.0 <1.0 Dibromoacetic acid 70 120 7.6 36

Bromate, μg/l 68 < 1 < 1 < 1

As seen in Table 7.2.1-1 DBP leve l significantly depends on TSS level (biocide demand due to organics) and chlorine dose.MEPC 59/2/11 ANNEX Page 51

I:\MEPC\59\2-11.doc The second series of tests was carried out by th e NIOZ personnel using s eawater collected from the North Sea, Texel harbour, in June to A ugust (ìsummerî water). Every day during the following 5 days after the chlorine addition, each sample was tested for ORP, FAH and TRO. After days 3 and 5, samples of the treated wate r were collected and sent for analysis of disinfection by-products using cold packs and overnight delivery to the US EPA accredited environmental laboratories. A summary of these results is presented in Table 7.2.1-2.

Table 7.2.1-2: Results of tests with North Sea water

* Tribromoacetic acid wasnít evaluated at that time. Th e data shown are an estimate based on an increased chlorine demand.

** One hour after treatment.

As seen from the table, the highe st chlorine dose used in the ìsummerî tests was at 5.6 mg/l. On a day 5 after the treatment TRO has dropped to about 0.1 mg/l, while after day 1 it was at about 0.5 mg/l.

Results listed in the table above were used for selecting Relevant Chemicals.

There was no toxicity testing done with the treated water at this time, as it is expected that using a full-size system in land-based tests will resu lt in lower TRO and DBP levels. Therefore, a thorough toxicity testing programme is planned for land-based a nd shipboard in respect to the chronic and acute toxicity of the treated water. Active Substances and DBP in Treated North Sea Water Biocide Dose Level, mg/l 2.7 3.62 5.6

Water Source

Description Date: August 14, 2008, pH=7.98, 18.5°C,

ORP=307 mV, TOC=1.15 mg/l Date: August 21, 2008, pH=7.93, 19°C, ORP=314 mV, TOC=1.48 mg/l Date: July 7, 2008, pH=8.00, 18°C, ORP=226 mV, TOC -unknown 1 h Biocide Demand, mg/l 1.92 2.51 4.36
Days after treatment 0** 1 3 5 0** 1 3 5 0** 1 3 5 TRO, mg/l 0.78 0.24 0.15 0.06 1.01 0.30 0.19 0.11 1.24 0.55 0.23 0.13 FAH, mg/l 0.49 0.11 0.07 0.03 0.69 0.16 0.10 0.10 0.74 0.24 0.11 0.07 Total THM, μg/l 21.2 11.3 41.7 18.7 88.3 40.6

Trichloromethane <0.4 <0.4 <0.4 <0.4 <0.4 <0.4 Tribromomethane 21.2 10.8 40.4 18.1 84.8 38.7 Bromodichloromethane <0.4 <0.4 <0.4 <0.4 <0.4 <0.4 Dibromochloromethane <0.2 <0.2 1.3 0.6 2.9 <0.2 Total HAA, μg/l 52.2 43.7 47.8 43.9 105* 91*

Chloroacetic acid <2.0 <2.0 <2.0 <2.0 <2.0 <2.0 Dichloroacetic acid 2.2 1.5 2.2 1.5 <1.0 <1.0 Trichloroacetic acid <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 Bromoacetic acid <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 Dibromoacetic acid 20 9.2 6.6 4.4 45 38 Tribromoacetic acid 32 33 39 38 60* 53* Bromate, μg/l 47 51 76 62 47 48MEPC 59/2/11 ANNEX Page 52

I:\MEPC\59\2-11.doc 7.2.2 Determination of holding time (G9: 5.2.7)

Holding time ñ the time the treated ballast wate r has to be retained in the tanks prior to discharge ñ serves two purposes with the SiCUREô system:

- to provide enough contact time for disinfection of ballast water; and - to allow the Active Substances to decay to a level that is environmentally safe for the discharge of treated water. Bench-top investigation showed th at disinfection can be complete within the first 24 hours after treatment. The environmental aspect of the holding time determination is more complex and requires analysis of such parameters as, residu al concentration of Activ e Substance in ballast water, its decay rate, and evaluati on of PEC, PNEC and their ratio.

While the latter are addressed in the Risk Assessme nt section of the Dossier , this section will be dedicated to evaluation of the pr edicted decay rate of the Active Substance (TRO) under real life conditions.

Decay rate of the halogen based TRO in seawater , and especially in indus trial port water, is difficult to define as there are se veral factors affecting it in the real life scenario. Among these are chlorine demand, photolytic a nd heat decomposition processes.

SWT has an extensive worldwide experience in pr oviding chlorine based technical solutions for biofouling control of land-based power stations, o ffshore platforms, and refineries, as well as for shipboard applications. From our experience, chlorine demand is, by far, the most important factor.

Chlorine demand, Dx, is the difference betwee n a halogen dose and TRO at the end of the contact time X.

Chlorine demand in polluted water has been studied extensively; the synopsis of that work is presented in White 1992. That work conducted in 1950s by Feben and Taras showed that there was a definite mathematical relationship betw een the amount of chlorine consumed in one contact period and that amount consumed in any othe r period. In general, this can be described as:

D = k t n

Where: D = chlorine demand mg/l (c hlorine dose ñ chlorine residual) t = chlorine contact time in hours k = chlorine demand after one hour mg/l n = slope of experimental curve.

More detailed TRO profiles for tests with chlo rine dose of 5.6 and 2.7 mg/l presented in Table 7.2.1-2 are presented in Tables 7.2.2-1 a nd 7.2.2-2 below, along with the calculated halogen demand.

Table 7.2.2-1: Results with chlorine dose of 5.6 mg/l

Time, h 0 0.25 1 24 48 72 96 120 TRO, mg/l 5.64 1.39 1.24 0.55 0.36 0.23 0.21 0.13 Demand, mg/l 4.25 4.4 5.09 5.28 5.41 5.43 5.51MEPC 59/2/11 ANNEX Page 53

I:\MEPC\59\2-11.doc Table 7.2.2-2: Results with chlorine dose of 2.7 mg/l

Time, h 0 0.25 1 24 48 72 96 120 TRO, mg/l 2.7 0.58 0.78 0.24 0.22 0.15 0.06 0.06 Demand, mg/l 2.12 1.92 2.46 2.48 2.55 2.64 2.64

The data from tables above were plotted on a log scale chart presented in Figure 7.2.2-1. The following models were then de rived from the plotted data:

For a dose of 5.6 mg/l (high demand) D t = 4.40 x t 0.047 For a dose of 2.7 mg/l (low demand) D t = 1.92 x t 0.058

The derived models were used to calculate the halogen demand and the corresponding TRO levels to determine the half- life of the Active Subs tance in North Sea water off Texel Island.

The results are presented i n Figures 7.2.2-2 and 7.2.2-3.

1 10

0.1 1 10 100 1000
Contact time, hoursDemand, mg/l 5.6 mg/l

2.7 mg/l

Figure 7.2.2-1: Halogen demand vs. cont act period in logarithmic scales.

Dose 5.6 mg/l

0 1 2 3 4 5 6

-50 -40 -30 -20 -10 0 10
Log (Time, hours)TRO, mg/l Model Test data

Figure 7.2.2-2: Model and experimental results for 5.6 mg/l doseMEPC 59/2/11 ANNEX Page 54

I:\MEPC\59\2-11.doc Dose 2.7 mg/l

0.0 0.5 1.0 1.5 2.0 2.5 3.0

-50 -40 -30 -20 -10 0 10
Log (Time, hours)TRO, mg/l Model Test data

. Figure 7.2.2-3: Model and experimental results for 2.7 mg/l dose

As seen from the figures above, calculated half-lives of TRO at the initial dose levels of 5.6 mg/l (a greater demand case) and 2.7 mg/l (a lo wer demand case) were found to be 10 -4 hour and 10 -3 hour, correspondingly. That is less than 1 second.

In conclusion, it should be noted that the same methodology will be followed during the land-based testing. TRO analysis will be perfor med more frequently duri ng the first 48 hours of the holding time in order to collect sufficient quantity of the reliable data to confirm our preliminary estimates of the TRO half-life in polluted seawater.

Table 7.2.2-3 shows observed TRO c oncentration in 1:1 volume mix of untreated, low chlorine demand seawater from North Sea collected in December and treated water with TRO at about 0.5 mg/l.

Table 7.2.2-3: TRO after mixing treated water with untreated water in volume ratio 1:1

The results of this test show that even with a dilution f actor as low as 2, th e half-life of TRO is less than 1 minute. With greater dilution rates it would be reasonable to a ssume that the half-life could be even lower. TRO in the mix after certain time, mg/l TRO in treated water prior to mixing, mg/l 1 min 6 min 12 min 20 min 35 min 60 min 0.49 0.12 0.09 0.08 0.05 0.04 0.03 0.49 0.12 0.08 0.05 0.07 0.05 0.03 0.52 0.13 0.09 0.07 0.06 0.04 0.03MEPC 59/2/11 ANNEX Page 55

I:\MEPC\59\2-11.doc 7.3 Risk characteri z ation and analysis (G9: 5.3)

7.3.1 Reaction with organic matter (G9: 4.2.1.3)

Major reactions of chlori ne with organic matter in polluted wa ter were described in section 4.3.4. The yield of THM and HAA identified as the majo r by-products of these re actions is directly related to the total organic carbon in the water being treated and the chlorine dose level used for disinfection. As these by-products may present a risk potential to the environment, their yields have to be minimized.

As it was shown in section 7.2.1, employing a variable, on-demand chlorine dosing allows minimizing their concentra tions in the treated water and, as a result, in the a quatic environment after discharge. On the other hand, the same r eactions result in a quick decay of the residual chlorine in the ballast tanks. Use of variable, on-demand chlorine dosing allows minimizing the level of TRO in the treated water. The same react ions will also play a very important role of eliminating chlorine from the treated wate r being discharged in to the port harbour.

7.3.2 Characterization of degradat ion route and rate (G9: 5.3.5)

In section 7.2.2 it was shown using the Feben and Taras model that due to a chlorine demand in the receiving water, the half -life of TRO could be as short as less than 1 second.

Figure 7.3.2-1 below shows the highest TRO levels in the treated water observed in preliminary test (See section 7.2.1) for 24, 48, 72, 96 and 120 hours after chlorine addition to the North Sea water sample. It also provides results of regr ession analysis of the data using an exponential decay equation.

The exponential decay equation predicts the dose leve l for this set of data at 0.733 mg/l, while the actual dose level was at 5.6 mg/l. The difference of about 4.9 mg/l then represents a consumption of chlorine at time zero caused by the chlorine demand. When chlorine demand has been met, then chlorine decay rates significantly slow down.

Degradation of TRO therefore has two major routes:

- through a quick consumption or decomposition by the chlorine demand in the polluted water (organic and nitrogen compounds, ions of Fe, Ni, Co that decompose TRO) ñ ìchlorine demand decay rateî; and

- through a slow decay via photolytic or heat decomposition ñ decay rate.

According to the calculations presented in sectio n 7.2.2, the ìchlorine dema ndî half-life of TRO is:

Chlorine Demandî Half-Life <1 second.

According to the data in Fi g. 7.3.2-1, during a holding period of from 24 to 120 hours the halflife of TRO due to a pho tolytic decomposition is:

Decay Half-Life = Ln(2)/0.0143 = 48 hours.MEPC 59/2/11 ANNEX Page 56

I:\MEPC\59\2-11.doc 

### y = 0.7328e -0.0143x



### R 2 

### = 0.9704

0 1 2 3 4 5 6

0 20 40 60 80 100 120 140
Holding Time, hoursTRO, mg/l

Figure 7.3.2-1: Test data and exponential decay model

7.3.3 Prediction of discharge and enviro nmental concentrations (G9: 5.3.8)

Introduction

The Marine Anti-foulant model (MAMPEC) was used in this dossier to predict environmental concentrations of TRO in the port water after discharge. MA MPEC was originally programmed to calculate environmental concentr ations of anti-fouling biocides released from ship coatings. In a modified way it can be used to calculate con centrations that are released constantly into the water by other processes like for example ballast wa ter treatment. The applicability of the model to any chemical substance made it a useful tool for environmental impact studies.

Active Substances and DBP

As a worst case scenario it was assumed in the model that all TRO is composed of the free available chlorine (FAC), by far the most toxic halogen compound. Further, the following calculations are therefore all based on HOCl (as sodium hypochlorite). PEC of DBP were calculated based on a dilution factor determined during MAMPEC simulation.

Parameterization of the model

To determine the environmental concentration of the released compound in the harbour water and the sediment, several parameters are necessar y. These parameters define the harbour and its characteristics, the compound that is being rele ased and the amount of ships and the amount of the specified compound released by those ships. This section pr ovides detailed parameterization of the model.MEPC 59/2/11 ANNEX Page 57

I:\MEPC\59\2-11.doc Compound definitions

TRO Molecular mass: 74.44 g·mol -1 Saturated vapour pressure at 20°C [Pa]: 23 Pa Solubility at 23°C 942 g·L -1 Octanol-water partition coe fficient [10 log Kow]: -0,87 Partition coefficient Koc [10 log Koc (l kg/OC)]: * -0.209 Acid dissociation constant pKa : 7.5 Henryís constant at 20°C [Pa m3 / mol]: * 1.82·10 - 2 Melting temperature [°C]: 18-25°C

* not available and therefor e estimated with MAMPEC

Half life

For modeling of various environmental scenarios a wide range of the half life was used, from seconds to days. Within MAMPEC it was not po ssible to include the de cay of the compound of interest during emptying the ballast water tank. In this case, ther efore, a worst cas e scenario was assumed that the water released from the ballast tanks has the same concentration at the start and at the end of discharge.

TRO concentrations in the ballast wat er and amount of ballast water released

The measurements in the treated ballast water during preliminary tests revealed the following concentrations of TRO in the tank (see Table 7.2.2-1):

start 5.60 mg·l-1 after 24 hours 0.55 mg·l-1 after 48 hours 0.36 mg·l-1 after 72 hours 0.23 mg·l-1 after 96 hours 0.21 mg·l-1

The following discharge TRO concentra tions were used in calculations:

- 0.13 mg/l - a concentration observed in tr eated water 120 hours after treatment; and - 0.55 mg/l - a concentration observed in treated water 24 hour s after treatment.

Further it was assumed that 1, 10 or 80 ships are present in the harbour and that all ships are equipped with the SiCUREô BWM system with the water characterized by the same holding ti m e (TRO level)

. It was assumed that there were 80 ships anchor ed in the Port of Rotterdam on an average day, discharging 397,000 (three hundred ninety thousand) m 3 /day or about 16,540 m 3 / hour of ballast water into the harbour. These numbers for the Port of Rotterdam were used in the publicly available dossiers of other BWMS developers an d it would be reasonable to maintain the same scenarios in the current calculations.

The following model inputs result from the assumptions above.MEPC 59/2/11 ANNEX Page 58

I:\MEPC\59\2-11.doc No. of ships Concentration of HOCl [mg·l -1 ] ballast water released per day [m3] HOCl released per day [g] 1 0.13 4,962 645 10 0.13 49,625 6,451 80 0.13 397,000 51,610 1 0.55 4,962 2,729 10 0.55 49,625 27,294 80 0.55 397,000 218,350

Harbour definitions

For all runs the OECD-EU commercial harbour wa s chosen with the default settings given by MAMPEC.

tidal period 12.41 h silt concentration 35 mg·l-1 POC 1 mg OC l-1 DOC 2 mg·l-1 chlorophyll 3 μg·l-1 salinity 34 pSU temperature 15°C latitude 50° N pH 7.5 depth mixed sediment layer 0.2 m sediment density 1,000 kg·m -3 org C in sediment 0.03 sedimentation velocity. 1 m·s -1 Exchange volume 5.1117·10 7 m3 · tide -1

x1 = 1,000 m y1 = 1,000 m x2 = 5,000 m y2 = 500 m depth = 15 m x3 = 2,500 m flow velocity 1 m·s-1

Background concentration

The background concentration of HOCL was assume d to be 0 to determine exactly the amount introduced by the SiCUREô BWM system.MEPC 59/2/11 ANNEX Page 59

I:\MEPC\59\2-11.doc Results of Modeling

Modeling was carried out for a single ship as the results can be linearly scaled up for the total

nu m ber of ships in the harbour. The res u lts of modeling are p r esented in Table 7.3.3-1, Figures 7.3.3-1 and 7.3.3-2.

The model simulation results show that the tota l amount of HOCl in port after discharge is mainly made up by the soluble fraction. The susp ended fraction in all c onsidered scenarios was below 0.002%.

Table 7.3.3-1: MAMPEC modeling results

PEC TRO, μg/l TRO in Discharge ñ 0.13 mg/l PEC TRO, μg/l TRO in Discharge ñ 0.55 mg/l Half-life, h

average minimum maximum average minimum maximum
0.0083 1.78E-06 8.70E-08 5.35E-06 6.75E-06 3.63E-07 7.50E-06
0.0167 3.19E-06 3.19E-07 3.54E-06 1.35E-05 1.35E-06 1.50E-05
0.25 4.71E-05 2.48E-05 5.31E-05 2.00E-04 1.05E-04 2.25E-04
0.5 9.29E-05 6.11E-05 1.06E-04 3.93E-04 2.59E-04 4.48E-04
1 1.80E-04 1.17E-04 2.09E-04 7.64E-04 4.94E-04 8.85E-04
2 3.44E-04 1.81E-04 4.10E-04 1.45E-03 7.66E-04 1.74E-03
3 4.94E-04 2.29E-04 6.08E-04 2.09E-03 9.69E-04 2.56E-03
4 6.35E-04 2.68E-04 8.03E-04 2.69E-03 1.13E-03 3.39E-03
5 7.66E-04 2.99E-04 9.96E-04 3.24E-03 1.26E-03 4.21E-03
6 8.91E-04 3.26E-04 1.19E-03 3.78E-03 1.38E-03 5.03E-03
7 1.01E-03 3.50E-04 1.38E-03 4.28E-03 1.48E-03 5.84E-03
8 1.12E-03 3.70E-04 1.58E-03 4.75E-03 1.56E-03 6.65E-03
9 1.23E-03 3.89E-04 1.76E-03 5.21E-03 1.65E-03 7.46E-03
10 1.34E-03 4.05E-04 1.95E-03 5.65E-03 1.71E-03 8.28E-03
16.56 1.96E-03 4.80E-04 3.21E-03 8.29E-03 2.03E-03 1.36E-02
24 2.55E-03 5.26E-04 4.56E-03 1.08E-02 2.23E-03 1.93E-02
33.6 3.20E-03 5.63E-04 6.19E-03 1.35E-02 2.38E-03 2.62E-02
48 4.10E-03 5.96E-04 8.59E-03 1.74E-02 2.53E-03 3.63E-02
96 6.46E-03 6.41E-04 1.55E-02 2.73E-02 2.71E-03 6.56E-02
984 1.50E-02 6.88E-04 4.21E-02 6.35E-02 2.91E-03 1.78E-01
1008 1.50E-02 6.88E-04 4.21E-02 6.35E-02 2.91E-03 1.78E-01
1992 1.64E-02 6.90E-04 4.63E-02 6.93E-02 2.92E-03 1.96E-01
4800 1.79E-02 6.93E-04 5.14E-02 7.56E-02 2.93E-03 2.17E-01
8760 1.79E-02 6.93E-04 5.14E-02 7.56E-02 2.93E-03 2.17E-01MEPC 59/2/11 ANNEX Page 60

I:\MEPC\59\2-11.doc 0.00 0.01 0.02 0.03 0.04 0.05 0.06

0 0 1 10 100 1000 10000

Half-Life, hTRO PEC, μg/l
average

minimum

maximum

Figure 7.3.3-1: Results of MAMPEC modeling fo r one ship, PEC TRO vs. TRO half-life at discharge TRO of 0.13 mg/l. Half-lif e axe is in a logarithmic scale

0.00 0.05 0.10 0.15 0.20 0.25

0 0 1 10 100 1000 10000

Half-Life, hTRO PEC, μg/l
average

minimum

maximum

Figure 7.3.3-2: Results of MAMPEC modeling fo r one ship, PEC TRO vs. TRO half-life at discharge TRO of 0.55 mg/l. Half-lif e axe is in a logarithmic scale

Predicted environmental concentra tions of TRO (PEC TRO) based on the calculation with one ship vary significantly de pending on which value of the TRO half-life was select ed as a model parameter. For a half-life less than 4 hours and discharge concentrations betwee n 0.13 and 0.55 mg /l, a range of the average PEC values was between 3.2E-6 and 2.7E -3 μg/l. For a half-life greater than 4 hours and discharge concentrations be tween 0.13 and 0.55 mg/l, a range of the average PEC values was between 0.001 and 0.076 μg /l. Results show that in stagnant waters of the port (maximum values) the predicted environmental concentr ation may peak at 2 to 3X times that of the average value. At half-lives of greater than several thousand hours (equal to no apparent decay) the predicted environmental concentration approach es an asymptotic valu e. An asymptotic va lue of the predicted environmental TRO at infinite half-life (an assu mption of no decay) can be directly associated with a dilution factor. Based on the data provide d above, the dilution factor can be calculated as about 7,200 times for a single ship in port and about 90 times for 80 ships in port.MEPC 59/2/11 ANNEX Page 61

I:\MEPC\59\2-11.doc Analysis of the data presented in Table 7.3.3-1 underscores the importance of a properly selected half-life value. With a 1 hour chlorine demand of above 2 mg/l observed in preliminary tests (see Tables 7.2.1-2 and 7.2.2-3) most, if not all, of the discharged free available chlorine will dissipate within seconds or minutes.

The charts below show maximum values of PE C for total residual oxidant in the port water assuming that there are 1, 10 and 80 ships in port , all being equipped with the SiCUREô system and simultaneously discharging treated ballast wate r with the same holding time. It is expected that only about 10 ships in the port would actua lly be equipped with the SiCUREô system. Figure 7.3.3-3 presents the data fo r a half-life of 1 minute, Figur e 7.3.3-3 presents the data for a half-life of 30 minutes and Figure 7.3.3-4 presents the data for a ha lf-life of 1 hour for TRO in treated water at 0.55 mg/l (1 day holding time) and 0.13 mg/l (5 days holding time).

0.0000 0.0002 0.0004 0.0006 0.0008 0.0010 0.0012 0.0014

1 10 80 Number of ships in harborPEC TRO, μg/l 0.13 mg/l

0.55 mg/l

Figure 7.3.3-3: Maximum concentration of TRO in the harbour calculated for 1, 10 and 80 ships for a half-life of 1 minute.

0.0000 0.0050 0.0100 0.0150 0.0200 0.0250 0.0300 0.0350 0.0400

1 10 80 Number of ships in harborPEC TRO, μg/l 0.13 mg/l

0.55 mg/l

Figure 7.3.3-4: Average concentration of TRO in the harbour calculated for 1, 10 and 80 ships for half-life of 30 minutesMEPC 59/2/11 ANNEX Page 62

I:\MEPC\59\2-11.doc 0.0000 0.0100 0.0200 0.0300 0.0400 0.0500 0.0600 0.0700 0.0800

1 10 80 Number of ships in harborPEC TRO, μg/l 0.13 mg/l

0.55 mg/l

Figure 7.3.3-5: Average concentration of TRO in the harbour calculated for 1, 10 and 80 ships for half-life of 1 hour

The final results of the predicted environmen tal concentrations of TRO for the worst case scenario of 80 ships in the harbour are summari zed in the Table 7.3.3.-2 be low for the wide range of half-life values.

Table 7.3.3-2: Summary of PEC calculations for 80 ships

Maximum PEC, μg/l at a Half-Life of TRO in Treated Water, mg/l 1 min 30 min 1 h 4 h 24 h 48 h 0.55 (1 day holding time) 0.001 0.036 0.071 0.2.70 1.50 2.90 0.13 (5 days holding time) 0.003 0.008 0.017 0.064 0.370 0.68

Predicted environmental concentr ations of DBP for the worst cas e scenario of 80 ships in the harbour are summarized in Table 7.3.3.-3 assuming no decay, 90 times dilution factor and maximum discharge concentrations reported in Table 3.2-1.

Table 7.3.3-3: Disinfection by-products

PEC, μg/l DBP Fresh water* Salt water Trihalomethanes:

Trichloromethane < 1 0 Dibromochloromethane 0 < 0.03 Tribromomethane 0 < 1 Haloacetic acids:

Dichloroacetic acid < 0.3 < 0.03 Trichloroacetic acid < 0.4 0 Dibromoacetic acid 0 < 0.56 Tribromoacetic acid 0 < 0.67 Sodium Bromate 0 < 0.7MEPC 59/2/11 ANNEX Page 63

I:\MEPC\59\2-11.doc SWT anticipates an extensive programme to determine the realistic decay rates of TRO and continue environmental modeling us ing models other than MAMPEC that take into consideration the effect of a chlorine demand. These result s will be used to define the SiCUREô BWMS environmentally safe holding tim e and will be provided for revi ew in a documentation to be submitted for Final Approval.

7.3.4 Assessment of potential fo r bioaccumulation (G9: 5.3.7)

The risk of bioaccumulation in freshwater and sa ltwater pelagic organisms as well as epifaunal sediment organisms is low ba sed on the log Pows of the Ac tive Substances and Relevant Chemicals which are <3 in all cases. The BCFs for the Active Substances and Relevant Chemicals reflect the low log Pows. All BCFs we re <100 L/kg which also indicates that little bioconcentration/bioaccumulation of the chemicals will occur. The risk to infaunal sediment organisms is low as well based on the Kocs which are all <500 L/kg and show that the chemicals will not readily partition to sediment and thus be of concern to benthic organisms residing in the sediment.

Likewise, the biomagnification of the Active Subs tances and Relevant Chemicals through aquatic food webs, wildlife, and humans is low based on th e log Pows and kocs. No data were found that suggest the Active Substances and Relevant Chem icals impart a foreign flavour or odour in the organisms exposed to the chemicals. Thus, consumers of seafood will not reject the seafood because of a flavour problem.

7.3.5 Effects assessment

The toxicity data sets (Tables 4.1.1-1 and 4.1.2-1) indicate that the risk of the Active Substances is negligible for most freshwater and saltwater predators (fish) and consumers (crustaceans) based on a chronic NOEC <0.01 mg/L using a worse case scenario of ballast water discharged into a port with no dilution and no additional decay of TRO. As discussed above (section 7.1.3); however, both the acute and chronic algal NOECs are based on unacceptable data that did not meet OECD 201 Guideline criteria. Thus, there is large uncertainty associated with the chronic primary producer data.

The ecological risk of the Relevant Chemicals to aquatic organisms is less clear than the risk from the Active Substances because much less chronic NOEC toxicity data are available. Sufficient chronic data are available for chloro form only to conclude that the compound should not be a risk to predators, consumers, and plants because all of the NOECs are 2-3 orders of magnitude above 0.01 mg/L.

Because of the lack of a comple te chronic database for (i.e., one or more of the three chronic trophic levels used in this dossier are not available), the acute toxi city database of the Relevant Chemicals provide additional data which may be us ed to access ecological risk to freshwater and saltwater organisms. Acute- to-chronic ratios (ACRs) have b een used in ecological risk assessments to extrapolate from acute responses to NOEC or chronic responses . This approach is based on the assumption that there is a relationsh ip between the response s in acute and chronic tests. Solomon et al. (2008), however, have made the point that this assumption is not necessarily true. For example, in an acute test the response may be lethality, whereas in the chronic test it may be growth or reproduction.MEPC 59/2/11 ANNEX Page 64

I:\MEPC\59\2-11.doc Lange et al. (1998) calculated ACRs for all aquatic species in the ECETOC aquatic database according to class of chemicals. For a number of species it was possible to calculate ACRs for five or more chemicals in a clas s. The maximum value for organics other than pest icides was 27.5. Uncertainty was shown to increase as the level of protection increased. Using the maximum ACR value of 27.5 to extrapolate from the acute data where sufficient data ar e available to provide chronic NOECs, one may estimate po tential risk for bromate, bromof orm, and trichloroacetic acid.

Bromate does not appear to be a risk to pl ants (8 mg/L) based on a chronic NOEC <0.01 mg/L under the worse case scenario give n above. If one uses an acute- to-chronic ratio (ACR) of 27.5, the acute bromate data for fish and crustac eans have an estimated chronic NOEC >1.0 mg/L which suggests that bromate will not be toxic to a ny of the three trophic levels considered in this dossier. Bromoform and trichloroacetic also do not appear to be a risk using the ACR of 27.5 to estimate chronic NOECs because the NOECs are 1-4 orders of magnitude above 0.01 mg/L. Sufficient chronic data and acute data to esti mate risk from ACRs are not available for the remainder of THMs and HAAs.

One acute fish value (34 mg/L) is available for dibromochloromethane whic h indicates that this THM may have similar toxicity pr operties and risk potential as th e other THMs in this dossier. Likewise, one acute fish value (106 mg/L) for dich loroacetic acid suggests that it may be similar to trichloroacetic acid. No acceptable acute or chronic data are available for dibromoacetic acid and tribromoacetic acid to make any conclusi ons regarding these HAAs. A great deal of uncertainty exists when one tries extrapolating ri sk from so little data. Additional uncertainty exists for some of the THMs and HAAs in that some of the acute concentrations were nominal measurements rather than measured concentrations . In addition, one must also consider the fact that it is unlikely that only one chemical will be discharged in the ballast water. Additional risks are likely when a mixture of the Relevant Chemicals is discharged.

7.3.6 Effects on aquatic organisms

The following PNECs were obtained using the a ssessment factors given in Table 2 of The Methodology for the information gathering a nd the conduct of work of the GESAMP-BWWG (IMO, 2008b).

Table 7.3.6-1: Predicted No-Effect Concentrat ion (PNEC) for the Active Substances and Relevant Chemicals in Freshwater and Saltwater

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

Active Substances TRO 0.04 N/A EU PNEC of 0.04 μg/L for HOCl was used because the value is more conservative than TRO HOCl 0.032 1,000 Lowest HOCl L(E)C50 from a fish, crustacean and algea Relevant Chemicals Bromate 8 1,000 Lowest L(E)C50 from a fish and alga THM -Chloroform 15 100 Lowest L( E)C50 and NOEC from a fish, crustacean, and alga THM -Bromoform 12 1,000 Lowest acute data from a fish, crustacean, and an algaMEPC 59/2/11 ANNEX Page 65

I:\MEPC\59\2-11.doc Chemical PNEC (μg/L) Factor Applied Comment(s)

THM -Dibromochloromethane 15 N/A Insufficient data; thus, aquatic PNEC taken from page 96 in EU (2007) HAA -Dichloroacetic acid 0.72 N/A PNEC taken from page 96 in EU (2007) HAA -Trichloroacetic acid 0.85 N/A PNEC taken from page 96 in EU (2007) HAA -Dibromoacetic acid 0.72 N/A PNEC was assumed to be the same value as that for dichloroacetic acid which was taken from page 96 in EU (2007) HAA -Tribromoacetic acid 0.85 N/A PNEC was assumed to be the same value as that for trichloroacetic acid which was taken from page 96 in EU (2007)

7.3.7 Effects on sediment

No acute or chronic whole sediment freshwater or saltwater toxicity data were found in the literature for the Active Substances or Releva nt Chemicals. The PNEC data for pelagic organisms can be used to estimate potential risks to epifaunal sediment organisms. As stated in section 7.3.4, the risk to infaunal sediment organisms is low based on the Kocs which are all <500 L/kg which indicate that the chemicals will not readily partition to sediment and thus be of concern to benthic organisms residing in the sediment.

7.3.8 Comparison of effect assessm ent with discharge toxicity

TRO and DBP concentrations in th e ballast water (see Table 7.2.1-2) five days after treatment exceed their corresponding PNECs (s ee Table 7.3.6-1). Based on the PNECs, the concentrations in the ballast tanks would be j udged to be an ecological risk wh en discharged with no further decay and mixing in the receiving harbour. As di scussed below in section 7.4; however, when the chlorinated ballast water is discharged and mi xed in Port of Rotterdam harbour water, aquatic risk is substantially reduced.

7.4 Risk to the aquatic environment

The potential risk to the aquatic environment is based on a series of PE C/PNEC ratios using a worst case scenario. The lowe st PNEC found in the risk ch aracterization was for the Active Substances (HOCl). The MAMPEC model was run using HOCl which is more toxic than any of the Relevant Substances. As a worst case scenario it was assumed that all TRO in the treated water was composed of HOCl and the model was run using HOCl concentrations of 0.55 and 0.13 mg/L for holding periods of 24 and 120 hours in the balla st water tanks, respectively, following initial treatment of the ballast water at 5.6 mg/L NaOCl. Various half-lives from 0.0083 hours (30 seconds) up to 48 hours were used as estimates of the decay caused by chlorine demand. In addition, it was assumed that up to 80 ships were present in the Port of Rotterdam in any given 24-h period.

Given below are the PEC/PNEC ratios for the av erage, minimum, and maximum concentrations of HOCl for 1 ship, 10 ships, and 80 ships in the Port of Rotterdam using the dilutions predicted by the MAMPEC model for various HOCl decay ha lf-lives (Tables 7.4-1, 7.4-2, and 7.4-3). The HOCl PNEC of 0.032 μg/l was used for the various half-life PEC/PN EC ratios in the tables below.MEPC 59/2/11 ANNEX Page 66

I:\MEPC\59\2-11.doc The PEC/PNEC ratios indicate that no aquatic risk (ratio <1) exists when 1 ship discharges an treated water after either 24 or 120 hours duration in a ballast ho lding tank following an initial chlorination of 5.60 mg/L HOCl and the residual Active Substance is subsequently mixed in the Port of Rotterdam with decay half-lives ranging from 0.0083 to 48 hours (Table 7.4-1).

The following risks to the aquatic environmen t are indicated from the PEC/PNEC ratios when 10 ships discharge HOCl and the Active Substa nce is mixed in the Port of Rotterdam with various half-lives. No risk is predicted when ballast water has been initially chlorinated with 5.60 mg/L HOCl held in the ballast water ta nks for 120 hours and subs equently discharged into the Port of Rotterdam at an average concentration of 0.13 mg/L with decay half-lives ranging from 0.0083 to 10 hours (Table 7.4-2). No risk is predicted when ballast water has been initially chlorinated with 5.60 mg/L HOCl held in the ballast water tanks for 24 hours and subsequently discharged into the Port of Rott erdam at an average co ncentration of 0.55 mg/L with decay half-lives ranging from 0.0083 hours up to 3 hours.

The following risks to the aquatic environmen t are indicated from the PEC/PNEC ratios when 80 ships discharge HOCl and the Active Substance is mixed in the Port of Rotterdam with various half-lives. No risk is predicted when ballast water has been initially chlorinated with 5.60 mg/L held in the ballast water tanks fo r 120 hours and subsequently discharged into the Port of Rotterdam at an average concentratio n of 0.13 mg/L with decay half-lives ranging from 0.0083 to 2 hours (Table 7.4.3). Risk is predicted for 80 ships at a half-life >0.5 hours when ballast water has been ini tially chlorinated with 5.60 mg/L HOC l, held in the ballast water tanks for 24 hours and subsequently discharged at an average concentratio n of 0.55 mg/L into the Port of Rotterdam.

As discussed in the risk characte rization section of this dossier, no risk is anticipated to infaunal sediment organisms. Very small concentrations of HOCl are predicted to occur in sediment in the Port of Rotterdam after a year of discharge from 80 ships per day in the harbour under any of the scenarios descried above.

Table 7.4-1: HOCl PEC/PNEC Ratios for discharged ballast water in the Port of Rotterdam for 1 ship

PEC/PNEC HOCl in Discharge ñ 0.13 mg/l PEC/PNEC HOCL in Discharge ñ 0.55 mg/l Half-life, h maximum average minimum maximum average minimum 0.0083 1.7E-04 5.5E-05 2.7E-06 2.3E-04 2.1E-04 1.1E-05 0.02 1.1E-04 1.0E-04 1.0E-05 4.7E-04 4.2E-04 4.2E-05 0.25 1.7E-03 1.5E-03 7.7E-04 7.0E-03 6.3E-03 1.4E-03

0.5 3.3E-03 2.9E-03 1.9E-03 1.4E-02 1.2E-02 8.1E-03

1 6.5E-03 5.6E-03 3.6E-03 2.8E-02 2.4E-02 1.5E-02 2 1.3E-02 1.1E-02 5.7E-06 5.4E-02 4.5E-02 2.4E-02 3 1.9E-02 1.5E-02 7.1E-03 8.0E-02 6.5E-02 3.0E-02 5 3.1E-02 2.4E-02 9.3E-03 1.3E-01 1.0E-01 3.9E-02 7 4.3E-02 3.2E-02 1.1E-02 1.8E-01 1.3E-01 4.6E-02 10 6.1E-02 4.2E-02 1.3E-02 2.6E-01 1.8E-01 5.4E-02 24 1.4E-01 8.0E-02 1.6E-02 6.0E-01 3.4E-01 7.0E-02 48 2.7E-01 1.3E-01 1.9E-02 1.1E+00 5.4E-01 7.9E-02MEPC 59/2/11 ANNEX Page 67

I:\MEPC\59\2-11.doc Table 7.4-2: HOCl PEC/PNEC Ratios for discharged ballast water in the Port of Rotterdam for 10 ships

Table 7.4-3: HOCl PEC/PNEC Ratios for discharged ballast water in the Port of Rotterdam for 80 ships

It is expected that PEC/PNEC ratios for Releva nt Chemicals will be below 1 taking into account dilution factor of 90 that were calculated for 80 ships discharging in th e port of Rotterdam (see Table 7.3.3-3) and PNEC values listed in Tabl e 7.3.6-1. Thus, it is exp ected that Relevant Chemicals will not present risk to the aquatic environment. The PEC/PNEC ratios for DBP are presented in Table 7.4-4 for a case of 80 ship s in the Port of Rotterdam assuming either freshwater or salt water scenario. PEC/PNEC HOCl in Discharge ñ 0.13 mg/l 10 ships PEC/PNEC HOCl in Discharge ñ 0.55 mg/l 10 ships Half-life, h

maximum average minimum maximum average minimum 0.0083 1.67E-03 5.55E-04 2.72E-05 2.3E-03 2.1E-03 1.1E-04 0.02 1.11E-03 9.96E-04 9.96E-05 4.7E-03 4.2E-03 4.2E-04 0.25 1.66E-02 1.47E-02 7.73E-03 7.0E-02 6.3E-02 1.4E-02

0.5 3.30E-02 2.90E-02 1.91E-02 1.4E-01 1.2E-01 8.1E-02

1 6.52E-02 5.63E-02 3.65E-02 2.8E-01 2.4E-01 1.5E-01 2 1.28E-01 1.07E-01 5.66E-05 5.4E-01 4.5E-01 2.4E-01 3 1.90E-01 1.54E-01 7.15E-02 8.0E-01 6.5E-01 3.0E-01 5 3.11E-01 2.39E-01 9.34E-02 1.3E+00 1.0E+00 3.9E-01 7 4.30E-01 3.16E-01 1.09E-01 1.8E+00 1.3E+00 4.6E-01 10 6.09E-01 4.18E-01 1.27E-01 2.6E+00 1.8E+00 5.4E-01 24 1.43E+00 7.97E-01 1.64E-01 6.0E+00 3.4E+00 7.0E-01 48 2.68E+00 1.28E+00 1.86E-01 1.1E+01 5.4E+00 7.9E-01

PEC/PNEC HOCl in Discharge ñ 0.13 mg/l 80 ships PEC/PNEC HOCl in Discharge ñ 0.55 mg/l 80 ships Half-life, h

maximum average minimum maximum average minimum 0.0083 1.3E-02 4.4E-03 2.2E-04 1.9E-02 1.7E-02 9.1E-04 0.02 8.8E-03 8.0E-03 8.0E-04 3.8E-02 3.4E-02 3.4E-03 0.25 1.3E-01 1.2E-01 6.2E-02 5.6E-01 5.0E-01 1.2E-01

0.5 2.6E-01 2.3E-01 1.5E-01 1.1E+00 9.8E-01 6.5E-01

1 5.2E-01 4.5E-01 2.9E-01 2.2E+00 1.9E+00 1.2E+00 2 1.0E+00 8.6E-01 4.5E-04 4.3E+00 3.6E+00 1.9E+00 3 1.5E+00 1.2E+00 5.7E-01 6.4E+00 5.2E+00 2.4E+00 5 2.5E+00 1.9E+00 7.5E-01 1.1E+01 8.1E+00 3.2E+00 7 3.4E+00 2.5E+00 8.8E-01 1.5E+01 1.1E+01 3.7E+00 10 4.9E+00 3.3E+00 1.0E+00 2.1E+01 1.4E+01 4.3E+00 24 1.1E+01 6.4E+00 1.3E+00 4.8E+01 2.7E+01 5.6E+00 48 2.1E+01 1.0E+01 1.5E+00 9.1E+01 4.3E+01 6.3E+00MEPC 59/2/11 ANNEX Page 68

I:\MEPC\59\2-11.doc Table 7.4-4: DBP PEC/PNEC Ratio s for Discharged Ballast Water in the Port of Rotterdam for 80 ships

PEC/PNEC DBP
Fresh water* Salt water

Trihalomethanes:

Trichloromethane < 0.07 N/A

Dibromochloromethan

e N/A < 0.002

Tribromomethane N/A < 0.07

Haloacetic acids:

Dichloroacetic acid < 0.42 < 0.04

Trichloroacetic acid < 0.47 N/A

Dibromoacetic acid N/A < 0.78

Tribromoacetic acid N/A < 0.79

Sodium Bromate N/A < 0.09

8 RISK ASSESSMENT

8.1 Risk to safety of ship

A Risk Ass e ss m ent is a m ethod used to esti m ate t h e likelihood of adverse effects to hu m an healt h and the environment, based on toxicity and expo sure information. The Risk Assessment section discusses potential risks to the safety of the sh ip, as well as potential exposures and risks to human populations who could potentially come in to contact with balla st water containing chemicals from the SiCUREô system.

8.1.1 Flooding

The SiCUREô system is installed such that the ships ballasting system can run independently of its operation. The connection to the ballast wate r piping system is made via class approved automatic valves. In case of catastrophic failu re of any of the components of the SiCUREô system, the emergency stop would automatically close these valves resulting in complete isolation from the ships ballast water piping.

8.1.2 Corrosion

Siemens intends to carry out a comprehensive corrosion testing programme as a part of its evaluation of the effects the SiCUREô system will have on ship safety. This section presents a brief review of the published data on corrosion of steel in seawater treated with HOCl. We believe that these data show that the contro l logic the SiCUREô BWM system is based on (variable, on-demand HOCl dosing), will minimize any potential for shipís safety due to corrosion and for the ships with long voyage time of several weeks and may even reduce that potential by inhibiting microbia lly induced corrosion (MIC).MEPC 59/2/11 ANNEX Page 69

I:\MEPC\59\2-11.doc The data on impact of chlorine additions to sea water on corrosion rates of the materials for shipboard use is very limited. Published results are mostly related to off-shore drilling applications, vary significantly a nd are difficult to summarize due to a variety of used techniques, test conditions, exposure times and mathematical models used to calculate an annual corrosion rate which is typically measured in millimetres or inches per year.

The most extensive publicly av ailable database published by The Tanker Structure Cooperative Forum establishes corr osion rates of the untreated ba llast water tanks in the range between 0.1 to 1.2 mm/year (BMT 2002).

The majority of the publicly available studies focusing on the effect of chlorine on corrosion rates have been performed employing accelerated co rrosion testing methods. Typical test time in these tests would be in an order of a few weeks. Test results would then be treated in accordance with a mathematical model to estimat e corrosion rates on an annual basis.

For example in one report (BMT 2002), corrosion tes ting in seawater in pres ence of chlorine was performed in a special apparatus where electrica lly isolated mild steel coupons were placed on a rotating wheel, submersed into sea water and submersed onto the sediment as well as placed in a dump atmosphere. Each test lasted for 15 da ys with chlorine bei ng added every 24 hours to constitute TRC of 10 and 40 ppm. Chlorine was quickly decomposing during these tests providing typical TRC of about 2 ppm.

In each experiment, the highest corrosion rates we re in those test coupons mounted on the wheel (conditions that can be found in ballast water pumps and pipes) , followed by those continually submerged under water surfaces (balla st water tanks), then those in the damp atmosphere (ballast water tanks) and finally the lowest corrosion rates were experienced by test coupons in the buried samples (ballast tanks bottoms covered with se diment). This result demonstrates that:

- the removal of corrosion products through work increase corrosion, i.e., the wheel provides the highest corrosion; and

- the availability of oxygen limits corrosion, i.e., the buried samples exhibited least corrosion.

The equivalent annual corrosion rates when adjust ed from the measured thickness loss incurred by the samples in the test apparatus were found to be between 0.1 mm/y in the buried/humid test coupons to 3 mm/y in the salt water test coupons on th e wheel. This represents a 3-fold increase over the results reported by The Tanker Struct ure Cooperative Forum, which was a maximum corrosion rate of 1.2 mm/y.

Based on this data, the report then makes an assu mption on the basis of the operational scenario of a 30 day cycle ballast water tr eatment and that during that cycl e the structure will be exposed to 2 days of high sodium hypochlorite dose and 4 da ys at a low dose (20% of total time) reducing chlorine levels to zero over time, the effective co rrosion rate of bare expo sed steel (after removal or damage to the coating system) in the ballast tank would be increased by 1% and its serviceable life reduced accordingly.

It is safe however to assume that addition of ch lorine will provide its major impact on corrosion rate of the pumps and pipes duri ng the ballasting operations and the approach used in Ballast Water Evaluation report (BMT 2002) may not be corre ct as it doesnít take into account localized corrosion, such as crevice corrosion.MEPC 59/2/11 ANNEX Page 70

I:\MEPC\59\2-11.doc Another article (Ventura 1989) discusses effect of chlorine additi ons on localized corrosion rate of stainless steel pipes with natural sea water flowing at 1.5 m/s. In these tests that lasted 75 days, both electrically isolated pipes and joint pipes of different steel gr ades were tested at chlorine concentrations of 0 (untreated seaw ater), 0.1 to 0.2 ppm and 1to 2 ppm.

The first series of tests with electrically isolated pipes has show n no traces of localized corrosion. Free corrosion potentials measured for each pipe being in a passive state have provided the following results:

- untreated seawater ñ within 15 days th e free corrosion potentials have increased from -100 to 0 mV (vs. Standard Elect rode (SCE)) to 300+/- 50 mV due to microbiologically induced corrosion (MIC);

- 0.1 to 0.2 ppm ñ free corrosion potential ha s immediately stabilized at 300+/-50 mV (vs. SCE); and

- 1 to 2 ppm ñ free corrosion potential ha s immediately stabilized at 560+/-60 mV (vs. SCE).

Free corrosion potential of steel in 1 to 2 ppm chlo rine in seawater has risen significantly to the levels when steel would start corrode, which was further confirmed in the tests with joint pipes made of dissimilate materials:

Table 8.1.2-1: Effect of chlorine concentration on corrosion of st ainless steel tubes in seawater

% of pipes with crevice corrosion Day
Untreated 0.1 ñ 0.2 ppm 1 ñ 2 ppm 1 0 0 100% 3 0 10% 100% 5 0 40% 100% 10 30% 100% 100% 25 100% 100% 100%

Most importantly, corrosion propa gation rates presented in this study in a form of galvanic currents for localized corrosion show that:

- untreated seawater ñ within 4 to 5 days galvanic current has increased from 1 μA
to 300 μA;

- 0.1 to 0.2 ppm ñ galvanic current was stable at 1μA during all 75 days o f testing; and

- 1 to 2 ppm ñ galvanic current was stable at 10 to 60 μA.

MIC is known to have a significant effect on co rrosion of the ballast water tanks. Different studies show that MIC rate can be as high as 12 to 100 mm/y - well a bove the corrosion rate limits reported by The Tanker St ructure Cooperative Forum.

Assuming average MIC rate at 60 mm/y and th e galvanic ratio presen ted in this study for untreated seawater and seawater with 1 to 2 ppm chlorine, localized corrosion rate can be estimated at 2 to 12 mm/y.MEPC 59/2/11 ANNEX Page 71

I:\MEPC\59\2-11.doc Itís also important to note that at TRC of 0.1to 0.2 ppm corrosion rate is reduced by about two orders of magnitude in comparison with th e corrosion rate observed in untreated seawater.

This conclusion is also supported in other report that shows re duction in corrosion rates at low chlorine residuals. They also note that th e corrosion rates obtained in artificial seawater (no marine organisms) are known to be lower than in real seawater (with marine organisms) and attribute this phenomenon to MIC.

Thus, chlorine concentration has a significant imp act on corrosion of the ballast tanks and needs to be minimized. The SiCUREô BWM system is designed to address this issue while providing needed disinfection.

Tests results presented in Table 7.2.1-2 show that when treated wa ter with high and low chlorine demand was treated to an ORP le vel of about 750 mV, the chlorine dose levels were at 5.7 and 2.7, correspondingly. However, just 15 minutes after the addition when all chlorine demand was met, the residual concentra tion of free chlorine in the treat ed water was about 1 mg/l and 24 hours after ñ just about 0.2 mg/l in both cases.

Figure 8.1.2-1: Corrosion Potential vs Chlorine Concentration (Redrawn from Reference (3))

Therefore, the SiCUREô treatment w ill have a minimal effect on corr osion of the ship materials. Moreover, if a duty cycle of chlorination is taken into the a ccount, those ships that have a long voyage time (transoceanic vessels) may even benefit from the SiCUREô treatment due to reduced corrosion rates caused by microbially induced corrosion.

The variable on-demand chlorine dosing design of the SiCUREô system allows for using the minimum amount of chlorine needed to achieve the required results. The amount of corrosive hypochlorite in the ballast tanks and associated piping will be kept at a minimum due to the control logic of the system. It may be expected that the corrosion rate may even decrease as a result of the ballast water trea tment using SiCUREô BWM system.

8.1.3 Fire/explosion

As the SiCUREô system does not require the st orage of any chemicals on board, there is no associated fire/explosion risk. The generation of sodium hypochlorite in-situ eliminates the need for chemical storage, however does result in the generation of hydroge n gas. The system includes a degas tank with air blowers and hydrogen gas detecting instrument ation to ensure that the hydrogen gas has been safely d iluted with air prior to venting.MEPC 59/2/11 ANNEX Page 72

I:\MEPC\59\2-11.doc 8.1.4 Accidental chemical release

Under normal operations, the SiCUREô system does not require the storage of any chemicals on board, therefore there is little associated risk of accidental chemical release. The generation of sodium hypochlorite in-situ results in the gene ration of hydrogen gas. Under normal operations, the generator cells do not leak or release hydrogen. In each electrolyser enclosure, the base area forms a drip tray to catch spillage from a failed cel l or piping seal. The base area has spillage probes to alarm if water is present. These probe s are set at 3 mm from the base. The cells have both flow and pressure sensors. The release of any hydrogen gas will be from the product water as it leaks from the failed seal. This occurs as the hydrogen by-product is entrained in the process water in very fine bubbles due to the hi gh flow rate and pressure. For hydrogen to be released only as a gas would require very low fl ow and pressure to allo w formation of localized gas pockets and a failure of a seal at that point. For this low flow and low pressure both the flow sensor and the pressure sensors would have had to have failed to function on sensing a fault condition. Therefore, three major failures mu st occur for release of hydrogen. Should an insignificant leak occur which doe s not provide sufficent water volu me to be detected the small volume of diluted hydrogen is allowed to safely vent.

8.2 Risk to h u man healt h

This section discusses potential exposure pathwa ys and risk to human populations who could be exposed to chemicals associated with the SiCUREô system. This section identifies the chemicals that will be considered, discusses pote ntial exposures to people who may be affected, and discusses the potential of adverse health effects.

8.2.1 Identification of chemicals of potential concern and sources

The chemicals of potential concern (COPCs) rela ted to the SiCUREô system include the Active Substances, which are hypochlor ous acid, chloramine, hypobromous acid and bromamine, and Relevant Chemicals, which are chloroform, dibr omochloromethane, bromoform, dichloroacetic acid, trichloroacetic acid, dibromoacetic acid, tr ibromoacetic acid and bromate. The Relevant Chemicals may be formed in small amounts as disinfection by-products.

The Active Substances are produced in-situ and inje cted directly into the ballast water piping system. The Relevant Chemicals are produced as by-products in the ballast water. There are no external sources of chemicals.

8.2.2 Exposure assessment

The Exposure Assessment consists of identifying human populations that could be exposed
to COPCs, and the exposure pathways through which they could have contact with COPCs. A co m plete exposure pathway consists of:

.1 a source or chemical release from a source; .2 an exposure point where contact can occur; and .3 an exposure route by which contact can o ccur (such as ingestion or inhalation)

. All of these components need to be pr esent for a complete exposure pathway.

This section discusses potenti al human populations who could be exposed to COPCs in the ballast water. This section al so identifies whether a complete exposure pathway exists for each of these population groups.MEPC 59/2/11 ANNEX Page 73

I:\MEPC\59\2-11.doc Technician/shipís crew

Technicians or shipís crew would not be expect ed to contact COPCs under normal operations. In the SiCUREô system, sodium hypochlorite is produced in-situ and injected directly into the ballast water piping system. The other COPCs would be formed as by-products in the ballast water. The potential for human exposure to concentrated levels of hypochlorite would only exist during a failure of the system or when performing service on the system. The risks associated with these scenarios are mitigated by numerous system safe ties (leak detection, hydrogen removal, equipment isolation, stray current protection, interlocks , etc.) and by following the use of appropriate personal protective equipment when performing maintenance and/or repair on the system.

The hydrogen gas produced by the SiCUREô system remains entrained in the seawater until it reaches the degas tank where it is diluted with air an d vented to a safe area. Leak detectors in the generator enclosure en sure that in a case of a leak, hydrogen levels will remain well below a safe limit. There is a potential for exposure to hydrogen gas during maintenance access to tanks however this is minimized by following stan dard shipboard procedur es for entering any tank/confined space, specifi cally gas free certification.

Under normal circumstances, there is no complete exposure pathway for this population group. However, for the purposes of this risk assessment, it was assumed that several times during the year, a technician could have expo sure to ballast water. A typica l incidental ingestion rate for water is 0.01 L/hour, which is one-fifth the amount that the United States Environmental Protection Agency (USEPA, 1989) assu mes is ingested during swimming (which is 0. 05 L/hr). It was also assumed that the technician could have exposure to the ballast wa ter for 10 events over the course of a year, and that exposure would la st no more than 1 hour per event. Therefore, these factors were used to modi fy drinking water guidelines, wh ich assumed daily ingestion of water at a rate of 2L/day. The follo wing modification fact or was calculated:

7,300 10days/yr 365days/yr

event day 0.01liter/ 2liter/day

= ×

This modification factor was used to modify drinking water guidelines developed by the World Health Organization (WHO, 2006) and USEPA (U SEPA, 2006). The dri nking water guidelines are derived to be protective of all potable uses of the water, including ba thing, cooking, as well as consumption as drinking water. The comparis on to the drinking water guidelines and the riskbased modifications is described in section 8.2.3.

Passengers

Passengers would not be expected to contact COPCs under normal operations. Since sodium hypochlorite is produced in-situ, ther e is little potential for accide ntal chemical release. There are numerous system safeties in place to mitigate a system failure. There is little potential for this population group to be exposed directly to treated ballast water. Therefore, no complete exposure pathways were identified for this group.

Employees in harbours

Employees in harbours have li ttle potential for exposure because of the low possibility of accidental release of sodium hypochlorite vap ours and hydrogen gas. There is also little possibility for this group to be exposed direc tly to ballast water. Therefore, no complete exposure pathways were identified for this group.MEPC 59/2/11 ANNEX Page 74

I:\MEPC\59\2-11.doc Bathers

Bathers in the harbour areas coul d potentially be exposed to released ballast water. COPC concentrations in ballast water would be greatly diluted in the sea water to which bathers could be exposed. Even though a complete exposure pa thway exists for this group, there is little possibility of adverse health effects since the COPC concentrations would be greatly diluted when treated ballast water is released into the sea. In addition, as discussed in section 8.2.3, the measured ballast water concentrations of vari ous chemicals were generally lower than their respective drinking water guidelines. Therefore, no adverse health effects would be expected from bathers exposed to diluted c oncentrations of these chemicals.

Consumers of seafood

Consumers of seafood from the harbour area wh ere the ballast water may be released are unlikely to be exposed to COPCs, since the COPCs are not expected to bioaccumulate in seafood. The COPCs are not expected to exhi bit biomagnifications or bioaccumulations, and subsequently would not be expected to persist in the food web. The United Kingdom Department for Environment Food and Rural Affairs (DEFRA) defines a bioaccumulative chemical as having a log K ow (octanol-water partition co efficient) greater than 4 ( http://www.defra.gov.uk/ENVIRONMENT/ch emicals/csf/criteria/detailed.htm ). The COPCs evaluated here all have log K ow s less than 4. Therefore, no complete exposure pathways were identified for this population group.

8.2.3 Potential exposure health risks

Various mammalian toxic endpoints for the COPC s are noted in Tables 4.2.1-1 through 4.2.8-1. To evaluate risks to a specific population, it is important to account for the toxic potency of the chemical, as well as the extent and duration of expos ure. As discussed previously, there is little potential for exposure for th e identified population groups.

As shown in Table 4.2.1-1, there is a wide range of acute LD50s. Most of the COPCs have the potential to be irritating to the eyes and ski n, as shown in Table 4.2.2-1. As shown in Tables 4.2.3-1 and 4.2.4-1, some of the COPCs result in a dverse effects to the liv er and kidney at the higher doses, and there are some reproductive effect s generally at high dose s (Table 4.2.5-1). As shown in Table 4.2.6-1, most of the COPCs are classified for carcinogenicity in IARC Group 3 (not classifiable as to carcinogenicity to human s). Chloroform and bromate are classified in IARC Group 2 B (possibly carcinogenic to humans).

The possibility of exposure health risks is very low because of the low potential for exposure to the COPCs. Possible exposure pathways includ e inhalation exposure duri ng accidental releases of sodium hypochlorite and hydrogen, and direct contact with ballast water. The possibility of inhalation exposure to sodium hypo chlorite and hydrogen gas is low, since this type of exposure would only occur during a failure of the system and there are numerous safety mechanisms in place to prevent exposure under these circumstances.

There is little potential for any of the population gr oups to be exposed directly to treated ballast water. However, for the purposes of this risk assessment, it was assumed that several times during the year, a technician could have exposure to ballast water. As described in section 8.2.1, a modification factor of 7,300 was used to modi fy drinking water guidelines developed by WHO (WHO, 2006) and USEPA (USEPA, 2006). Tabl e 8.2.3-1 shows concentrations of various chemicals in treated North Sea water samples at day 5 after treatment. Table 8.2.3-1 also shows drinking water guidelines devel oped by WHO and USEPA. Drinking water gui delines are basedMEPC 59/2/11 ANNEX Page 75

I:\MEPC\59\2-11.doc on daily ingestion exposure, and are designed to be protective of all water uses, including ingestion, dermal contact and inhalation of vola tiles in the household. As shown in Table 8.2.3-1, the concentrations of TRO (total oxidant, su m of hypochlorous acid and chloramines) and FAH are less than the drinking wa ter guideline for hypochlorous acid. Amongst the detected chemicals, the only chemicals that slightly excee d the guidelines are bromate and total haloacetic acid (which only has a USEPA drinking water guidelin e). All of the other detected chemicals are less than the WHO and USEPA dri nking water guidelines. Table 8.2.3-1 also shows risk-based criteria that are the drinking water guidelines modified by the factor of 7,300 which represents a more reasonable, but still conservative, exposure scenario. The measured concentrations of the various chemicals are all lower than the risk-based criteria. These results indicate that in the unlikely event of a shipís technician contacting th e ballast water several times over the course of the year, adverse health effects are not expected.

It is possible, however, that th ere might be acute effects from occasional exposure. The USEPA (USEPA, 2006), has developed one-d ay drinking water health adviso ries for a child, that may be used to gain some idea of the potential for ac ute effects. The one-day health advisory for bromate is 0.2 mg/L and for total THM is 4 mg /L. The measured bromate (0.062 mg/L) and THM (0.0406 mg/l) concentrations are lower than th e one-day health adviso ries. These results indicate that there is no potenti al for acute health risks base d on exposure to ballast water.

Table 8.2.3-1: Comparison of ballast water concentrations to ri sk-based criteria

R isk-based Criteria B ased on Likely E xposure Scenari o ( e ) C hem

ical (m g/L)

TR

O 0.55 5 (h) 4.0 (c)(h) N o 29200 N o FAH 0.24 5 (h) 4.0 (c)(h) N o 29200 N o

Brom ate 0.062 0.01 (j) 0.01 (c) Y es 73 N o TR

O 0.13 5 (h) 4.0 (c)(h) N o 29200 N o FAH 0.10 5 (h) 4.0 (c)(h) N o 29200 N o Total TH M 0.0406 NA 0.08 (c) N o 584 N o Trichlorom ethane N D 0.3 0.08 (d)(g)(l)(l) N D N D N D Tribromomethane 0.0387 0.1 0.08 (d)(g)(m )(l) N o 584 N o Bromodichlorom ethane N D 0.06 0.08 (d)(g) N D 438 N D D

ibrom ochlorom ethane 0.0006 0.10 0.08 (d)(g) N o 584 N o Total H A A 0.091 (i) NA 0.06 (c)(f) Y es 438 N o C

hloroacetic acid N D 0.02 (k) 0.06 (d)(f) N D 146 N D D

ichloroacetic acid 0.0015 0.05 (j) 0.06 (d)(f) N o 365 N o Trichloroacetic acid N D 0.20 0.06 (d)(f) N D 438 N D Bromoacetic acid N D NA 0.06 (c)(f) N D 438 N D D

ibrom oacetic acid 0.038 NA 0.06 (c)(f) N o 438 N o Tribromoacetic acid 0.053 (i) NA N A N o N A N o N otes: FAH

- Free available halogen (hypochlorous acid; no chloroam ines). H AA - Haloacetic acids. N A - N ot available; not analyzed. N D - N

ot detected. TH

M - Trihalom ethanes. TR

O - Total oxidant (sum of hypochlorous acid and chloroam ines). (a) Treated N orth Sea w ater samples collected July and/or A ugust 2008. M axim

um

concentration at specified day after treatm ent (i.e., at day 1 or day 5). (b) World Health O rganization (W H O), 2006. G uidelines for Drinking Water Quality, 3rd. Edition. 2006. (c) U nited States E nvironm ental Protection Agency. O ffice of Water. N ational Prim ary D rinking Water M axim

um

C

ontam inant Levels (M CLs). 2003. (d) U nited States Environm ental Protection A gency. 2006 Edition of the D rinking W ater Standards and H ealth Advisories. 2006. (e) R isk-based criteria calculated assuming an incidental ingestion rate of 0.01 L/day and an exposure frequency of 10 days/year. T he low est guideline value for each com pound w as multiplied by a factor of 7300 ([2L / 0.01L] x [365 days / 10 days]) to adjust guideline values for a site-specific exposure scenario. (f) V

alue for five haloacetic acids (m onochloroacetic acid, dichloroacetic acid, trichloroacetic acid, brom oacetic acid and dibrom oacetic acid). (g) Value for total trihalom ethanes (chloroform , brom odichlorom ethane, dibrom ochlorom ethane and bromoform). (h) Value for chlorine used (as a surrogate for hypochlorous acid). (i) Tribrom oacetic acid w as not evaluated for this particular collection tim e; value show n is an estim ate based on an increased chlorine dem and. (j) Provisional value. (k) V

alue for monochloroacetic acid. (l) Value under review

. W ater Source C oncentration E xceeds R isk-based C riteria? Day after treatm ent: 1

Da

y after treatm ent: 5 U SEP

A D

rinking W ater Guidelines (c) (d) ( m

g /L

) W

ater Source C oncentration (a)

( m

g /L ) W H O D

rinking W ater Guidelines (b)

( m

g /L

) Water S ource Concentration Exceed s a Guideline Value?MEPC 59/2/11 ANNEX Page 76

I:\MEPC\59\2-11.doc 8.2.4 Risk characterization

The Exposure Assessment section identified various population gr oups who could potentially be exposed to COPCs. There is a low possibility of exposure for all of the population groups. The technicians/shipís crew have some potential fo r inhalation exposure during accidental releases of sodium hypochlorite and hydrogen. However, this type of exposure would only occur during a failure of the system and there are numerous safety mechanisms in place to prevent exposure under these circumstances. Any exposure to trea ted ballast water would be limited to occasional maintenance activities.

In the unlikely event that a ship technician was required to contact the treated ballast water, a comparison of risk-based criteria (derived to be protective of occasional contact with the treated ballast water) with chemical concentrations measur ed in tests of treated ballast water indicates that a technician would not experience adverse h ealth effects (measured chemical concentrations were all lower than the risk-based criteria). This group would also wear appropriate PPE during any maintenance activities; therefore the actu al possibility of exposure is very low.

8.3 Risks to the aquatic e n vironment

Siemens have identified TRO as the most toxic chemical in the treated water and conducted an environmental risk analysis based on the PEC/PNEC ratios. These ratios were calculated for a ìtypicalî European port such as the Port of Rotterdam using MAMPEC model and assuming 1, 10 or 80 ships in port, all e quipped with the SiCUREô BWM systems and simultaneously discharging ballast water with the same holding time of 120 and 24 hours.

Siemens have used the published TRO PNEC data of 0.04 μg/l. The analysis has shown that PEC/PNEC ratio for TRO is strongly affected by the value of a half- life model parameter.

When chlorine demand is taken into account, (half-life times of less than 0.5 ho ur) PEC/PNEC ratios were calculated at less than 1.0 for the treated wate r with the holding time of 24 and 120 hours or more.

When no chlorine demand is taken into account, (h alf-life times of greater than about 48 hours) PEC/PNEC ratios were calculated as greater than 1.0 for the trea ted water with the holding time of 24 and 120 hours.

For one ship the PEC/PNEC ratios were calc ulated as less than 1.0 for practically all environmental scenarios.

The analysis has shown that during the land-based and shipboard testing a special attention has to be paid to identifying a realistic decay rate of the TRO in order to be able to calculate PEC with a greater level of certainty.

Analysis of the environmental data has also sh own that in the absence of any decay rate, the dilution rate in the harbour of a ìtypicalî European port is somewhere around 7,200 times for a single ship and about 90 tim es for 80 ships in port.

Use of a variable, on-demand chlorine dosing us ing SiCUREô control logic allows minimizing generation of such disinfection by-products as THM, HAA and sodium bromate. Their concentrations in treated water were found to be less than 100, 50 and 50 μg/l, correspondingly. PNEC for these compounds calculated assuming an assessment factor of 1,000 were found to be at 0.25 ñ 25 μg/l. With a dilution factor of 90 to 7,200, none of these co mpounds are expected to present any risk to the aquatic environment.MEPC 59/2/11 ANNEX Page 77

I:\MEPC\59\2-11.doc 9 Assessment Report

9.1 Overvie w o f data and endpoints

All of the chemicals were eval uated with regard to aquatic and mammalian toxicity. The evaluation of aquatic toxicity included assessing the chemicals with regard to persistence, bioaccumulation and toxicity. The Active Substances (TRO, hypochlorous and hypobromous acids) are not persistent. All of the Relevant Chemicals are persistent using Procedure (G9) criteria of a half-life >60 days in marine water or >40 days in freshwater. None of the Active Substances or Relevant Chemicals are expected to bioaccumulate using Procedure (G9) criteria of a log Pow <3. Therefore, the chemicals are not expected to accumulate in the tissue of marine organisms. The chronic toxicity database in this dossier indicates that none of the Active Substances appear to be toxi c to fish (0.04 mg/L) and crus taceans (0.012 mg/L) based on a chronic NOEC criterion of <0.01 mg/L. The Active Substances may have the potential to be toxic to algae based on unacce ptable OECD data when the chronic NOEC criterion of <0.01 mg/L is used. The chronic toxicity da tabase shows for the Relevant Chemicals for which acceptable OECD chronic toxicity data ar e available (bromate a nd two THMs) that these compounds are much less toxic than the Active S ubstances. There are no studies indicating the possibility of endocrine disrupti on for any of these chemicals.

The evaluation of mammalian toxicity involved assessing the chemicals for various endpoints, including acute and chronic toxici ty, carcinogenicity, and developmenta l effects. There is a wide range of acute toxicity. Most of the COPCs have the potential to be irritating to the eyes and skin, however these effects were seen at higher c oncentrations than would be present in ballast water. The toxicity studies show that some of the COPCs result in adve rse effects to the liver and kidney at the higher doses, an d there are some reproductive eff ects generally at high doses. It is unlikely that people could be exposed to c oncentrations that could result in adverse health effects. A comparison of the measured ballast water concentrations of various chemicals to drinking water guidelines showed that the measur ed concentrations were generally lower than their respective drinking water guidelines. Th erefore, no adverse he alth effects would be expected from exposures that are much less than daily drinking water exposure. The low bioaccumulation potential for these chemicals indi cates that consumers of seafood in the harbour areas would not face health risks from c onsuming seafood containing these chemicals.

Therefore, the possibility of exposure health ri sks for human populations is very low because of the low potential for exposure to the COPCs. The SiCUREô system can safely and effectively treat ballast water in compliance with the guidelin es. It is important to note that this basic process has been used for a long time to disinfect drinking water and bathing water. There have been many toxicology studies conducted on both the Active Substances and the disinfection by-products to develop health-prote ctive guidelines for these chem icals. The potential risks to the safety of ships, human health and the enviro nment are expected to be low because of the low potential for exposure. In the SiCUREô syst em, sodium hypochlorite is produced in-situ and injected directly into the ballast water piping system. The other COPCs would be formed as by-products in the ballast water. Therefore, no chem icals are stored on board, thereby reducing the possibility of accidental releas e. There is little potential for exposure to ballast water.

9.2 Test report data quality

The test reports used in this a pplication were from a variety of reputable s ources, including the International Programme on Chemical Safety (a consortium of governmental bodies including the World Health Organization and the United Nations Environment Programme), theMEPC 59/2/11 ANNEX Page 78

I:\MEPC\59\2-11.doc International Agency for Research on Cancer, and the United States National Library of Medicine. The studies included in reports by these agen cies are valid and repr oducible studies. The toxicology studies followed st andard laboratory practices.

REFERENCES

Aldrich Chemical MSDS. Chlorodibromomethane. http://hazard.com/msds/f2/bkk/bkkxv.html

.
Anderson, D.R., R.M. Bean, and C.I. Gibson. 1979. Biocide By-P roducts in Aquatic Environments Annual Report C overing Period October 1, 1977 Through September 30, 1978. NUREG/CR-0504. U.S. Nuclear Regula tory Commission, Washington, DC.

Authur. J.W., R.W. Andres, V. R. Mattson, D.T. Olson, G.E. Glass, B.J. Halligan and C.T. Walbridge. 1975. Comparative Toxicity of Sewage-Effluent Disinf ection to Freshwater Aquatic Life. EPA-600/3-75-012. U.S. Envi ronmental Protection Agency, Duluth, MN.

BMT Fleet Technology Ltd, 2002. Ballast Wa ter Treatment Evaluation Using Copper and Sodium Hypochlorite as Ballast Water Biocides, Final Report.

Brooks, A.S. and N.E. Liptak. 1979. The Effect of Intermittent Chlorination on Freshwater Phytoplankton. Water Res. 13:49-52.

California EPA. 2008. Chemical M eeting the Criteria for Listi ng as Causing Cancer via the Authoritative Bodies Mechan ism: Dibromoacetic Acid. http://www.oehha.org/Prop65/CRNR_notices/admin_ listing/intent_to_lis t/pdf_zip/NOIL_ABPkg 32a_dibromoacetic%20acid.pdf

.
Carlson, S., 1991. Fundamentals of Wa ter Disinfection, Nuremberg, Germany.

Cowgill, U.M., D.P. Milazzo, and B.D. Landenberg er. (1989). Toxicity of Nine Benchmark Chemicals to Skeletonema costatum , a Marine Diatom. Environ. Toxicol. Chem. 8:451-455.

Crecelius, E.A. 1979. Measurements of Oxidan ts in Ozonized Seawater and Some Biological Reactions. J. Fish. Res. Bd. Can. 36:1006-1008.

Dennis, W.H.J., E.P. Meier, W.F. Randall, A.B. Rosencrance, and D.H. Rosenblatt. 1979. 1993. Data taken from ECOTOX Database (Last Update June 2008), U.S. Environmental Protection Agency, Mid-Continent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

.
Erickson, S.J. and A.E. Freeman. 1978. Toxi city Screening of Fi fteen Chlorinated and Bromated Compounds Using Four Species of Marine Phytoplankton. Pages 307-310 in : Jolley, R.L. et al. (eds.). Water Chlorination Environmenta l Impact and Health Effects, Vol. 2, Ann Arbor Sci., Ann Arbor, MI.

EU Risk assessment report-Chlorine, 2007.

Fisher Scientific MSDS. Tribromoacetic acid. https://fscimage.fishe rsci.com/msds/58658.htm

.MEPC 59/2/11 ANNEX Page 79

I:\MEPC\59\2-11.doc Fisher, D.J., D.T. Burton, L.T. Yonkos, S.D. Turley, B.S. Turley, G.P. Ziegler, and E.J. Zillioux. 1994. Acute and Short-Term Chronic Effects of Continuous and Intermittent Chlorination on Mysidopsis bahia and Menidia beryllina . Environ. Toxicol. Chem. 13:1525-1534.

Fisher, D.J., D.T. Burton, L.T. Yonkos, S.D. Tu rley, and G.P. Ziegler. 1999. The Relative Acute Toxicity of Continuous a nd Intermittent Exposures of Chlo rine and Bromine to Aquatic Organism in the Presence and Absence of Ammonia. Water Research 33:760-768.

Foster, G.D. and R.E. Tullis. 1984. Data take n from ECOTOX Database (Last Update June 2008), U.S. Environmental Protection Agency, Mi d-Continent Ecology Di vision, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

. Goodman, L.R., D.P. Middaugh, D.J. Hansen, P.K. Higdon, and G.M. Cripe. 1983. Early Life-Stage Test with Tidewater Silversides ( Menidia peninsulae ) and Chlorine-Produced Oxidants. Environ. Toxicol. Chem. 2:337-342.

Hazardous Substances Databank, United St ates National Library of Medicine, http://www.toxnet.nlm.nih.gov ).

Helz, G.R. 1981. Chlorine Chemistry. Pages 7-50 in : Hall, L.W., Jr., G.R. Helz, and D.T. Burton (eds.). Power Plant Chlorinati on A Biological and Chemical Assessment. Ann Arbor Science Publishers, Inc., Ann Arbor, MI.

Hermanutz, R.O., K.N. Allen, and S.F. Hedtke. 1990. Toxicity and Fate of Total Residual Chlorine in Outdoor Experime ntal Streams. Pages 463-477 in : Jolley, R.L. et al. (eds.). Water Chlorination Environmental Impact and Health E ffects, Vol. 6, Ann Arbor Sci., Ann Arbor , MI.

Holland, G.A., J.E. Lasater, E.D. Newman, a nd W.E. Eldridge. 1960. Data taken from ECOTOX Database (Last Update June 2008), U.S. Environmental Protection Agency, MidContinent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

. Howard, P.H. (ed.). 1990. Ha ndbook of Environmental Fate a nd Exposure Data for Organic Chemicals, Volume II Solvents . Lewis Publ., Chelsea, MI.

Howard, P.H. (ed.). 1993. Ha ndbook of Environmental Fate a nd Exposure Data for Organic Chemicals, Volume IV Solvents 2. Lewis Publ., Chelsea, MI.

HSDB. 2008. Hazardous Substances Data Bank. National Library of Medicine. http://toxnet.nlm.nih.gov/

. IARC. 1999. International Agency for Resear ch on Cancer. Chloroform. VOL.: 73 (1999). http://www.inchem.org/documents/iarc/vol73/73-05.html

. IARC. 2004. International Agency for Resear ch on Cancer. Chloramine. VOL.: 84 (2004) (p. 295). http://www.inchem.org/documents/iarc/vol84/84-02-chloramine.html

. IMO (International Maritime Organi zation). 2008a. Marine Envi ronment Protection Committee. Procedure for approval of ballast water management systems that make use of Active Substances (G9). Resolution MEPC.169(57). MEPC 57/21, annex 1.MEPC 59/2/11 ANNEX Page 80

I:\MEPC\59\2-11.doc IMO (International Maritime Organization). 2008b. Harmful Aquatic Organisms in Ballast Water. MEPC 58/2/7, GESAMP-BWWG 6/9, annex 4. International Mari time Organization, London, United Kingdom.

IMO (International Maritime Organization). 2008c. Harmful Aquatic Organisms in Ballast Water. MEPC 58/2/7, GESAMP-BWWG 6/9, annex 5. International Mari time Organization, London, United Kingdom.

IMO (International Maritime Organization). 2008d. Harmful Aquatic Organisms in Ballast Water. MEPC 58/2/7, GESAMP-BWWG 6/9, anne x 6. International Maritime Organization, London, United Kingdom.

IMO (International Maritime Organization). 2008e. Harmful Aquatic Organisms in Ballast Water. MEPC 58/2/7, GESAMP-BWWG 6/9, annex 7. International Mari time Organization, London, United Kingdom.

IPCS. 2000. International Program me on Chemical Safety. Envir onmental Health Criteria, 216. Disinfectants and disinfectant by-produc ts. World Health Organization. http://www.inchem.org/documents/ehc/ehc/ehc216.htm#PartNumber:3

. IPCS. 2004. International Programme on Chemi cal Safety. Concise International Chemical Assessment Document 58.World Health Organization. http://www.inchem.org/documents/cicads/cicads/cicad58.htm

.

IPCS/ICSC. 2000. Dichloroacetic Acid. http://www.inchem.org/docum ents/icsc/icsc/eics0868.htm

.
Kuhn, R. 1988. Data taken from ECOTOX Database (Last Update June 2008), U.S. Environmental Protection Agency, Mi d-Continent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

.
Kuhn, R. and Pattard, M.. 1990. Data taken fr om ECOTOX Database (Last Update June 2008), United States Environmental Pr otection Agency, Mid-Continent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

.
Kuhn, R., Pattard, M., Pernak, K.D., and Winter, A. 1989. Data taken from ECOTOX Database (Last Update June 2008), United States. Envi ronmental Protection Agency, Mid-Continent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

. Lange, R., T. Hutchinson, N. Scholz, and J. Solbe. 1998. Data taken from Solomon et al. (2008). Analysis of the ECTOC Aquatic Toxicity (EAT) Database . II. Comparison of Acute to Chronic Ratios for Various Aquatic Organism s and Chemical Substances. Chemosphere 36:115-127.

LeBlanc, G.A. 1980. Data taken from EC OTOX Database (Last Update June 2008), U.S. Environmental Protection Agency, Mi d-Continent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

.
Lund, E., Oxidative Inactivation of Poliovirus, Virological Labor atory of the Department of Bacteriology, University of Gothenburg, and th e Virological Department of the Municipal Laboratories, Gothenburg, Sweden (1963).MEPC 59/2/11 ANNEX Page 81

I:\MEPC\59\2-11.doc Mallinkrodt Baker. 2006. Material Safety Data Sheet. Bromoform. http://www.jtbaker.com/msds/englishhtml/b4612.htm

.

Mallinkrodt Baker. 2006. Material Safety Data Sheet. Chloramine-T. http://www.jtbaker.com/msds/englishhtml/c2167.htm

.
Mattice, J.S., S.G. Tsai, and M.B Burch. 1981. Toxicity of Trihalomethanes to Common Carp Embryos. Trans. Amer. Fish. Soc. 110:261-269.

OECD SIDS. 2008. Trichloroacetic acid CAS nr. 76-03-9, UNEP Publications 174. http://www.inchem.org/documents/sids/sids/76039.pdf http://www.chem.unep.ch/irptc/sids/OECDSIDS/76039.pdf

.
Pratt, J.R., N.J. Bowers, B.R. Niederland, and J. Cairns. 1988. Effect of Chlorine on Microbial Communities in Naturally Derived Microcos ms. Environ. Toxicol. Chem. 7:679-687.

Rasmussen, V., Nissen, B., and Ebba Lund. A Comparison of Cryptosporidium, Giardia and Virus Inactivation Using Chlorine Residual an d Redox Monitoring, Laboratory of Virology and Immunology, Dept. of Veterinary Microbiol ogy, The Royal Veterinary and Agricaltural University, Copenhagen, Denmark, presen ted at AWWA 1994 ñ New York, (1994).

Richardson, L.B., D.T. Burton, and J.C. Rhoderick. 1981. Toxicity of Bromate to Striped Bass ( Saxatilis ) and Juvenile Spot ( Leiostomus xanthurus ). J. Toxicol. Environ. Health 8:687-695.

Sanders, J.S., J.H. Ryther, and J.H. Batchelder . 1981. Data taken from paper cited in the European Union Risk Assessment Report for Sodium Hypochlorite. Draft Report. November 26, 2007.

Saroglia, GM.G. and G. Scarano. 1979. Influene of Molting on the Sensitivity of Toxics to the Crustacean Penaeus kerathurus (Forskal). Ecotoxicol. Environ. Safety 3:310-320.

Siemens Stranco Products. The re lationship of ORP to PPM and It s Automatic Control, Aquatic Newsletter, v.1, #.3, (2007).

SIRI MSDS Index. http://hazard.com/msds/index.php

.
Solomon, K.R., T.C.M. Brock, D. de Zwart, S.D. Dyer, L. Posthuma, S.M. Richards, H. Sanderson, P.K. Sibley, and P.J. van den Br ink (eds). 2008. Extrapolation Practice for Ecotoxicological Effect Character ization of Chemicals. CRC Pr ess, Taylor & Francis Group, New York, NY.

State of Michigan, Department of Environmental Quality, Surface Water Quality Division Ballast Water Treatment Evaluation Using Coppe r and Sodium Hypochlorite as Ballast Water Biocides, Report, 12 April, 2002.

Thatcher, T.O. 1978. The Relative Sensitivity of Pacific Northwest Fishes and Invertebrates to Chlorinated Sea Water. Pages 341-350 in : Jolley, R.L. et al. (eds.). Water Chlorination Environmental Impact and Health Effects, Vol. 2, Ann Arbor Sci., Ann Arbor, MI.

TOXNET. 2008. U.S. National Library of Me dicine. Hazardous Substance Data Base. National Institutes of Medicine, Washington, DC. http://www.toxnet.nlm.nih.gov

.MEPC 59/2/11 ANNEX Page 82

I:\MEPC\59\2-11.doc Trenel, J. and R. Kuhn. 1982. Data taken fr om ECOTOX Database (Last Update June 2008), U.S. Environmental Protection Agency, Mi d-Continent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

. U.S. Environmental Protection Agency. 1978. Data taken from ECOTOX Database (Last Update June 2008), U.S. Environmental Protec tion Agency, Mid-Contin ent Ecology Division, Duluth, MN. http://www.epa.gov/med/Prods_Pubs/ecotox.htm

. USEPA Integrated Risk Information System (IRIS) http://cfpub.epa.gov/ncea/iris/index.cfm

.

USEPA. 1989. Risk Assessment Guidance for S uperfund: Volume I. Human Health Evaluation Manual (Part A). Interim Final. Office of Emergency and Remedial Response. U.S. Environmental Protection Agen cy, Washington, D.C. EPA 540/1-89/002. http://www.epa.gov/oswer/riskassessment/ragsa/

.

USEPA. 2006. 2006 Edition of the Drinking Water Standards and Health Advisories. EPA 822-R-06-013. Summer 2006. http://www.epa.gov/waterscience/c riteria/drinking/dwstandards.pdf

.
Ventura, G,. et.al . Effect of NaClO Biocide Additions in Natural Seawater on Stainless Steel Corrosion Resistance, CORROSION, Vol.45, No.4, 1989, pp. 319-325, (1989).

Victorin, K., Hellstrom, K. G. and Rylander, R. Redox Potential Measurements for Determining the Desinfection Power of Chlorinated Water, Dept. of Environmental Hygiene, The National Institute of Public Health and the Institute of Hygiene, Karolinska Institute, Stockholm, Sweden, (1971).

Videau, C., M. Khalanski, and M. Penot. 1979. Data taken from paper cited in the European Union Risk Assessment Report for Sodium Hypo chlorite. Draft Report. November 26, 2007.

White, G.C. The Handbook of Chlorination and Alternative Disinfectants, 3rd Edition, 1992, 218-220.

WHO. 2006. Guidelines to Dri nking Water Qual ity. 3rd Edition. 2006. http://www.who.int/water_sanit ation_health/dwq/gdwq3rev/en/

.

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