For reasons of economy, this document is printed in a limited number. Delegates are 

kindly asked to bring their copies to meetings 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 ORGANISMS 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-confidential 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 Convention for the Control and Management of 

Shipsí Ballast Water and Sediments stipulates that ballast water management systems that make 

use of Active Substances to comply with the Convention shall be approved by the Organization. 

2 The ìProcedure for approval of ballast water management systems that make use of 

Active Substances (G9)î stipulates the required information (MEPC 57/21, annex 1, paragraph 4.2.1) 

and provisions for risk characterisation and analysis (MEPC 57/21, annex 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 Germany has verified the application dossier 

and believes it satisfies the data requirements 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 application dossier in the annex. The complete 

dossier will be made available to the experts of the GESAMP-BWWG with the understanding of 

confidential treatment. 

Action requested of the Committee 

5 The Committee is invited to consider the proposal 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 SIEMENSí SiCUREô BWM SYSTEM 

2.1 Basics of chlorine disinfection relevant 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 plants, 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 effect 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 main metabolites in the relevant media 

4.3.4 Reaction with organic matter 

4.3.5 Potential physical effects on wildlife and benthic habitats 
MEPC 59/2/11 

ANNEX 

Page 2 

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

4.3.6 Potential residues in seafood 

4.3.7 Any known interactive effects 

4.4 Physical and chemical properties of the Active Substances, Relevant Chemicals and 

treated ballast water (G9: 4.2.1.4) 

4.5 Analytical methods at environmentally 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 control, 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 MATERIAL SAFETY DATA SHEETS 

(G9: 4.2.7) 

7 RISK CHARACTERIZATION 

7.1 Screening for persistence, bioaccumulation, 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 treated 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 degradation route and rate (G9: 5.3.5) 

7.3.3 Prediction of discharge and environmental 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 assessment with discharge toxicity 

7.4 Risk to the aquatic environment 
MEPC 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 

REFERENCES 
MEPC 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 Millivolt 
MEPC 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 Organization 
MEPC 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 Kocs for the Active Substances and Relevant Chemicals 

4.1.5-1 Log Pows 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 Available 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 water after 5 days retention time 

7.2.1-2 Results of tests with North Sea water 

7.2.2-1 Results with chlorine dose of 5.6 mg/L 

7.2.2-2 Results with chlorine 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 Ballast Water in the Port of Rotterdam for 

1 ship 

7.4-2 TRO PEC/PNEC Ratios for Discharged Ballast Water in the Port of Rotterdam for 

10 ships 

7.4-3 TRO PEC/PNEC Ratios for Discharged Ballast Water in the Port of Rotterdam for 

80 ships 

7.4-4 DBP TRO PEC/PNEC Ratios for Discharged Ballast Water in the Port of 

Rotterdam for 80 ships 

8.1.2-1 Effect of chlorine concentration on corrosion of stainless steel tubes in seawater 

8.2.3-1 Comparison of Ballast Water Concentrations to Risk-Based Criteria 
MEPC 59/2/11 

ANNEX 

Page 7 

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

Index of figures 

Figure Description 

1-1 SiCURETM BWM System 

2.1-1 Dissolution of hypochlorous acid vs. pH at different temperatures 

2.1-2 Ammonium and nitrate concentration in the 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 seawater with urea and glycine 

2.2-3 ORP vs. Free Chlorine and water pH 

2.2-4 ORP Readings in cooling water treated with chlorine on board LNG Carrier 

2.3-1 3-D model of containerized SiCUREô BWMS 

2.3-2 Concentric Tube Electrode of the ChloropacÆ cell 

2.3-3 ChloropacÆ 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 levels 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 levels 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-life 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-life axe is in a logarithmic scale 

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 

7.3.3-4 Average concentration of TRO in the harbour calculated for 1, 10 and 80 ships for 

half-life of 30 minutes 

7.3.3-5 Average concentration of TRO in the harbour 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 confidential part of the application.
MEPC 59/2/11 

ANNEX 

Page 8 

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

1 INTRODUCTION (CHLOROPAC AND SICURETM ñ A NATURAL EVOLUTION)

The Siemens SiCURETM Ballast Water Management (BWM) System utilizes proven technology 

to filter out, oxidize and disinfect aquatic invasive species (AIS) 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 shipboard installations. 

It has been found that the most efficient method of hypochlorination is to produce sodium 

hypochlorite in-situ, electrolytically, on demand, utilizing the Siemens 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 

ChloropacÆ. 

Siemens Water Technologies is a leading provider of hypochlorination and electrochemical 

equipment designed to control biological fouling and corrosion wherever seawater is used as 

cooling or process water. 

A division of the Siemens Industry Solutions group, Water Technologies capitalizes on 

world-class experience, technology, R&D support and manufacturing facilities of the group, 

which provides innovative solutions and services for 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 SiCURETM Ballast 

Water Management System. 

The SiCURETM BWM System that has several unique design features is based on the Chloropac

Electrochlorination System developed to prevent marine organisms from fouling seawater piping 

and heat exchangers on board ships, offshore facilities, and land-based petrochemical and electric 

utilities. Biofouling control using ChloropacÆ technology has become extremely popular within 

the maritime industry since with ChloropacÆ 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, 

ChloropacÆ plants were installed on offshore production platforms in the North Sea and in 1984 a 

Hazardous Area Certificate (BASEEFA) was issued for ChloropacÆ Electrochlorinators. 

Over 2,000 shipboard Chloropac Systems have been installed 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 cooling flow rates, reduced heat exchanger efficiency, and increased 

fuel and maintenance costs. 

The Chloropac System electrolyzes seawater to produce sodium hypochlorite, an ìActive 

Substanceî, on demand, in-situ directly from seawater without the addition or mixing of any 

other chemicals. 

The patent pending Siemens SiCURETM BWM System utilizes a proven Chloropac, Concentric 

Tube Electrode (CTE) Technology to produce sodium hypochlorite in sufficient quantity to 

completely eliminate AIS in the high volume ballast water systems on board (see Figure 1-1). 
MEPC 59/2/11 

ANNEX 

Page 9 

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

Figure 1-1: SiCURETM BWM System 

Unlike other BWM systems, SiCURETM is not based on a fixed chlorine 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 filtration and proprietary disinfection control. 

Pre-filtration of the ballast water is incorporated as part of the SiCURETM BWM system to 

remove bigger AIS and sediments. This allows the electrochlorinator to produce less NaOCl, 

i.e. only the minimum required concentration of NaOCl is produced. 

In addition the Siemens expertise in disinfection of swimming pools, wastewater and cooling 

towers and the latest developments in Oxidation Reduction Potential (ORP) technology led to the 

development of a proprietary control logic utilized 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 generation of disinfection by-products. 

The system is ready to be tested on a full, commercial scale in land-based and shipboard setting. 

Siemens believes that through the land-based and shipboard testing 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 ìGuidelines for approval of ballast water management 

systems (G8)î and will comply with the ìProcedure for approval of ballast water management 

systems that make use of Active Substances (G9)î. 

Filtration combined with Sodium Hypochlorite produced in-situ and injected based on demand is 

the logical choice for ballast water management: 

The main features of the SiCUREô 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 demonstrated 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 environmentally 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 unwanted possibly unsafe chemicals on board 

which will require special storage and handling by the crew; 

- SiCURETM BWMS Sodium Hypochlorite generators are low maintenance; CTE 

technology, utilizing centre taped cells to prevent stray currents in the ballast water; 

- SiCURETM BWMS modular design can accommodate any ballast water capacity; a 

singular system will be designed for a ballast water flow from 200 to 3,000 m3/h; 

- SiCURETM BWMS can be supplied as individual components to accommodate 

retro-fit applications on existing vessels as required; and 

- SiCURETM BWMS employs ìOn-Demandî hypochlorite dosing powered by Siemens 

proprietary ORP based control logic which allows automatic hypochlorite dosing 

depending on ballast water conditions. This minimizes residuals disinfection 

by-products (DBP) and corrosion. 

Siemens is applying for Basic Approval of the SiCURETM BWMS hypochlorination, its 

proprietary control technology combined with the filtration method of ballast water treatment in 

accordance with Procedure (G9) adopted by resolution MEPC.169(57). 

2 DESCRIPTION OF THE SIEMENSí SiCURETM 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 biocide 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 exposure. SiCUREô operation philosophy is based 

on on-demand dosing of chlorine produced in-situ from seawater. Biocide dosing is regulated to 

provide minimum required biocide levels to provide disinfection, while reducing its residual, 

disinfection by-products (DBP) and corrosion to the ship. The control logic of the SiCUREô 

system is based on the principles developed by a renowned microbiologist Dr. Ebba Lund 

discussed below in this section. These are the principles currently used for safe disinfection of 

swimming pools and other recreational facilities around the world. 

In order to provide a required level of disinfection for a shipboard ballast water application, itís very 

important to understand the chemistry 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 treatment applications, such as disinfection of 

drinking/potable water, recreational water reservoirs (swimming pools and spas), industrial and 

municipal cooling towers, wastewater, biofouling control of industrial equipment in power and 

oil and gas industries, as well as for disinfection of seawater desalination equipment. Experience 

gained in these areas is invaluable for designing an effective and robust ballast water treatment 

system for shipboard use. 

Chlorine dissolved in water instantly generates HOCl (hypochlorous acid) according to the 

equation (1): 

Cl2 + H2O ! 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 attacks 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 chlorine dose which is required for chlorine to be 

detected in the treated water is often called chlorine demand. Furthermore, chlorine may react 

with certain compounds to create chloramines, also a biocide that is much weaker than HOCl. 

Additional dosing of chlorine will lead to an increase in the chlorine concentration in water and 

will also lead to chlorine reacting with chloramines to produce nitrogen gas and chloride. Above 

certain levels, called breakpoint chlorination, all chlorine present in the water will be in the form 

of free chlorine, often called Free Available Chlorine (FAC) or Free Available Halogen (FAH). 

The breakpoint chlorination is used for treating ballast water where extremely 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 Chlorine or Total Residual Oxidant 

(TRO) and mistakenly used as a measure of the disinfection efficiency. If both chloramines and 

FAH are present in water, it is FAH that provides 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 very weak acid with an ionization 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, hypochlorite ions are a very weak oxidant, which makes undissociated 

HOCl the only biocide of importance. 

Disassociation of HOCl depends on several factors, 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 treatment 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 trends for chlorination of 

ballast water could be quite significant. While 

most of disinfection applications 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 water with pH very close to 7, while water in the 

Middle East and many other marine ports would be essentially seawater 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 seawater, 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, its dissociation constant pKa is about 8.5 against chlorineís pKa of 7.5, 

thus HOBr is more stable than chlorine under alkaline pH values. While this helps in 

disinfecting seawater, the HOBr availability 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 temperature of the ballast water may be changing 

significantly from season to season (e.g., due to rainfall) and from low to high tide within a single 

day. These changes will have a significant impact on the availability of undissociated 

hypohalogenous acid (HOCl and/or HOBr) and, as a result, the halogen dose required to provide 

the mandatory standards of treatment. 

pH is very important for disinfection of water with halogens. However, other water conditions 

in different ports around the world 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 Value

Species 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 freshwater or seawater 

environments, is determined by inorganic and organic pollutants in water, as well as by the 

biological load. The pollutants could be dissolved in water or be present in suspended solids of 

mineral or organic matter. The concentration of these 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 the 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 conditions, 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 conditions. If the chlorine dose 

level is not sufficient, disinfection will not be effective: 

if the chlorine dose selected is in excess of what is required, this 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 chlorine 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 electrons) of water being treated. 

The importance of ORP control for water sanitation was established when in 1963 a world-renowned 

microbiologist Ebba Lund authored a paper (Lund 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 chlorine
MEPC 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 reductants is constant, the 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 changed then only the redox potential may still be used. 

The oxidation potential is a measure of the oxidizing power of the oxidant, its ability to consume 

electrons. The stronger that ability of the oxidant, the higher is the oxidation potential (Siemens 

Stranco 2007). For example, an oxidation potential of free chlorine is 1.48 V, the oxidation 

potential of hypochlorite ion is just 0.84 V. The electrode 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 directed across the sensorís electrode tip for measurement of the 

water ORP. In clean water with no inorganic or organic load creating chlorine demand, the 

oxidizer in the water ìpullsî strongly on the electrons in the platinum or gold tipped sensor. The 

higher the oxidation potential of the latter, the harder 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 reductants). The oxidizer in the water draws its attention to this ready 

source of electrons and its oxidation strength towards viruses, bacteria, algae, etc., diminishes. 

The ìpullî on the sensorís electrons is also reduced, that will result in a reduced ORP value. 

In swimming pools the amount of reductants (urea, uric acid, organics 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 ensure the inactivation rate of 

viruses and or bacteria while maintaining a constant concentration level of free and combined 

chlorine will not ensure the necessary inactivation rate. This also means 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 below 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 main and has a bypass for ballast water discharge 

operations. The second stage is a proprietary disinfection with a biocide produced on board a 

ship in-situ from saltwater. Biocide that is predominantly a sodium hypochlorite solution 

produced electrochemically using a stand-alone electrochemical generator is injected into the 

ballast water on demand using proprietary control logic. On-demand biocide dosing is intended 

to significantly diminish corrosion and disinfection by-products issues as well as to minimize 

residual biocide concentration in ballast water discharge. 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 screen. Integration with the shipboard ballast system will include 

startup, shutdown, emergency shutdown and data acquisition communication 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 Logic Controller (PLC) 

programmed to initiate operation when all the system prerequisites for the operation are satisfied. 

The systemís mechanical equipment is: 

- Automatic Backwash Seawater Inlet Filter 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 ChloropacÆ electrochemical generator. The electrolyzer consists of 

a pre-determined number of cells arranged in series. 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 produce 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 (oxidation strength) of the ballast water. 

At the outlet of the electrochemical generator, seawater will contain several products of electrochemical 

reactions taking place at the anode and cathode surfaces of the CHLOROPAC generator. These are 

hypochlorous acid (HOCl) in equilibrium with hypochlorite ion (OCl-), hypobromous acid (HOBr) 

in equilibrium with hypobromous ion (OBr-

), certain short-life oxygenated chemical compounds 

and oxygen gas (O2) generated at the anode and hydrogen gas (H2) 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 the main ballast water flow, but rather in a 

side-stream flow of about 5.5 or 11 m3/h. The side-stream flow is selected based on the size of a 

system and is independent of the main ballast water flow. Resulting 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 and highly reactive oxygenated species, possibly including hydrogen 

peroxide and ozone, present in the stream will decompose. For example, hydrogen peroxide will 

be reduced to water by free available chlorine and ozone will decompose into oxygen gas with 

chlorine acting as a catalyst. Therefore, these oxygenated 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 produced, will depend on a size of the system. For 

example, the systems used for treating 200 m3

/h and 1,000 m3/h will use the same side-stream 

flow of 5.5 m3/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 variable biocide dosing, variable dose is achieved 

by maintaining the constant side-stream flow and varying the DC current from the transformerrectifier to meet a specific biocide demand. Therefore, the biocide 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 salinity 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 current 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 limited by the imposed DC current and voltage boundaries. 

Hydrogen gas and oxygen gas are completely removed in the degas tank, therefore they will be 

considered as by-products and not Relevant Chemicals. The list of Active Substances as produced 

by the SiCUREô BWMS and their expected concentration 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 carried 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 comprised of HOCl, when 

biocide is mixed with the ballast water the 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 halogenation agents and will react with certain 

nitrogen compounds such as ammonia, urea, aminoacids, etc., present in fresh or salt water 

generating chloramines and/or bromamines, 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 analyzed in the treated water, they typically 

analyzed together and reported as Free Available 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 treated ballast water using SiCURE BWMS process 

should be characterized as TRO. It is expected that in fresh water 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 concentrations 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 relevant 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 mix of FAH, combined chlorine, combined bromine, if any, measured as equivalent chlorine ** 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 Relevant Chemicals. Depending on a source 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 below. 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 Waterî. Siemens acknowledges that the referenced 

below list for Relevant Chemicals may be incomplete at this point and will be thoroughly 

investigated during land-based and shipboard testing. Concentration levels of certain Relevant 

Chemicals presented in the table 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 water2

Concentration, 

μg/l 

Chemical Name Formula Molecular 

Weight 

CAS 

Number 

Fresh 

water1

Salt 

water 

(bio)degradation 

rate or half-life 

Trihalomethanes: 

Trichloromethane CHCl3 119.38 67-66-3 < 90 03 From no decay to 

28 days 

Dibromochloromethane CHBrCl2 208.29 124-48-1 0 < 3 No decay 

Tribromomethane CHBr3 252.77 75-25-2 0 < 90 No decay 

Haloacetic acids: 

Dichloroacetic acid C2H2Cl2O2 128.94 79-43-6 < 30 < 3 > 60 days 

Trichloroacetic acid C2HCl3O2 163.39 76-03-9 < 33 0 > 60 days 

Dibromoacetic acid C2H2Br2O2 217.86 631-64-1 0 < 50 > 60 days 

Tribromoacetic acid C2HBr3O2 296.76 75-96-7 0 < 60 > 60 days 

Sodium Bromate NaBrO3 150.9 7789-38-0 0 < 80 > 60 days 

Note: 1 ñ Estimate. There were no tests performed to date with the fresh water. This will be addressed during 

land-based and shipboard testing. 

2 ñ During land-based testing halogen acetonitrile compounds will be also included for analysis and be

added to the list of potential Relevant Chemicals, if necessary. 

3 – Indicates concentration below the analytical detection limits. See section 4.5 for the detection limits. 

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

4.1 Data sets on effects on aquatic plants, 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 were selected to conform 

where possible with OECD Guidelines 203 (adopted 17 July 1992), 202 (adopted 13 April 2004), 

and 201 (adopted 23 March 2006), for fish, crustaceans, and algae, respectively. In some cases 

toxicity data could not be found that followed the OECD Guidelines. Thus, some toxicity data 

were taken 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 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 are the lowest toxicity values found in the 

literature for each of the test substances for fish, crustaceans, and algae. 

The literature summarized below for acute toxicity shows that TRO and HOCl are more toxic to fish 

and crustaceans relative to bromate, THMs, and HAAs (Table 4.1.1-1). For example, the acute 

toxicity of TRO and HOCl to fish and crustaceans 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; OECD 201 Guideline requirement) were found 
MEPC 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 algae than bromate, THMs, and HAAs. 

No relevant ecotoxicity data was found for HOBr because of the complexity 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. Siemens will investigate this further and carry out 

ecotoxicity testing with HOBr prior to Final Approval. 

Relative to the Active Substances, bromate 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 for 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 were found in the literature for 

the acute toxicity of dibromoacetic acid and tribromoacetic acid. 

Table 4.1.1-1: Acute aquatic toxicitya

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 survivalb 0.032 N/A Fisher et al.

(1999) TRO (Freshwater) 

A Natural 

phytoplankton 

47-h change in 

Chla

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 survivald

 0.062 N/A Fisher et al.

(1999) TRO (Saltwater) 

A Dunaliella 

primolecta 24-h growthe (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 literature 
MEPC 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 survivalg

 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 survivalg 30 N/A Foster and 

Tullis (1984) Chloroform 

A Scenedesmus 

subspicatus 48-h growthh

 (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 hatchi 

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 

immobilizationj 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 literature 
MEPC 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 Guidelines 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 requirements (Test Method 2021.0) for measuring the acute 

toxicity of effluents and receiving waters to Daphnia magna (U.S. EPA, 2002a). c Study did not meet OECD 201 Guidelines because the test evaluated a change in chlorophyll at 47 h rather than 

growth at 72 h. 

d Study did not meet OECD guidelines because the test evaluated survival at 96 h rather than immobilization at 48 h. 

However, the test did meet U.S. EPA regulatory test requirements (Test Method 2007.0) for measuring the acute 

toxicity of effluents and receiving waters to Mysidopsis bahia (U.S.EPA, 2002a). e Study did not meet OECD 201 Guidelines because the test evaluated a growth at 24 h rather than growth at 72 h. 

g Study did not meet OECD 202 Guidelines because the test evaluated survival 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 toxicity of effluents and receiving waters to a representative crustacean (U.S.EPA, 2002a). 

h Study did not meet OECD 201 Guidelines because the test evaluated 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 1001.0) 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 toxicity of effluents and receiving waters to a representative crustacean (U.S.EPA, 2002a). 

4.1.2 Chronic aquatic toxicity 

Chronic toxicity data for both the Active Substances and Relevant Chemicals were selected 

to conform where possible with OECD Guidelines 210 (adopted 17 July 1992), 211 

(adopted 3 October 2008), and 201 (adopted 23 March 2006), for fish, crustaceans, and algae, 

respectively. In some cases toxicity data could not be found that followed the OECD Guidelines. 

Thus, some toxicity data were used 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 toxicity. 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 for fish, crustaceans, and algae. 

The literature summarized below for chronic toxicity 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 potential toxicity also suggests that TRO is more 
MEPC 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 relative 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 approximately 2 to 3 orders 

of magnitude less toxic than TRO to fish, crustaceans, 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 chronic data could be found for fish, 

crustaceans, or algae exposed to dibromochloromethane. 

Only two chronic values were found in the literature for the four haloacetic acids under consideration 

in this dossier. An EC3 of 1485 mg/L was found for an alga exposed to dichloroacetic acid. 

The 7-day algal cell proliferation test does not meet the OECD 201 Guidelines which require a 

minimum 72-hour growth measurement as the endpoint. A NOEC of 200 mg/L has been 

reported for an alga exposed to trichloroacetic acid. 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 haloacetic acid algae values do not meet OECD 201 Guidelines, the 

values are given in Table 4.1.2-1 as an indication of potential chronic toxicity. No fish or 

crustacean chronic data were found for dichloroacetic acid or trichloroacetic acid. No chronic 

toxicity data of any type were found for dibromoacetic acid or tribromoacetic acid. 

Table 4.1.2-1: Chronic Aquatic Toxicitya

Test 

Substance 

F 

C 

A 

Species Test Type 

LC50/ 

EC50 

mg/L 

NOEC 

mg/L 

Reference/ 

Comments

Active Substances

F Ictalurus 

punctatus

134-d growthb 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 

biomassc

N/A (0.079) Pratt et al.

(1988) 

F Menidia 

peninsula

32-d egg to posthatchN/A 0.04 Goodman et al.

(1983) 

C Panaeus 

kerathurus 

7-d growth/moultingd N/A (0.079) Saroglia and 

Scarano (1979) TRO (Saltwater) 

A Natural 

phytoplankton

21-d reduction in cell 

densityc

N/A (0.001) Sanders et al.

(1981) 

F Oncorhynchus 

kisutch 

23-d survivale N/A 0.042 Holland et al.

(1960) 

C Americamysis 

bahia 

7-d reproductiond N/A 0.048 Fisher et al.

(1994) HOCl 

A No data found 

in literature 
MEPC 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 survivalf (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 

Dibromochloromethane 

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 proliferationg (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 

thresholdh

 (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 Guidelines or other accepted testing procedures but were 

included to provide an indication only of potential toxicity. 

b Study did not meet OECD 210 Guidelines because the test was initiated with juveniles rather than the egg 

stage. c Study did not meet OECD 201 Guidelines because the test did not have control culture biomass data. 

d Study did not meet OECD 211 Guidelines 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 Guidelines 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 Guidelines because the test used cell proliferation and as an endpoint rather 

than growth. 

h Study did not meet OECD 201 Guidelines 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 Substances (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 next 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 whole 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: Kocs for the Active Substances and Relevant Chemicals 

Chemical Koc (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 Substances and Relevant Chemicals are all <3 which indicate that 

significant bioconcentration/bioaccumulation (<100 L/kg wet weight for the whole organism 

at 6% fat) of the chemicals will not occur. Likewise, the BCFs also show that the potential for 

significant bioconcentration/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 Pows and BCFs for the Active Substances and Relevant Chemicals 

Chemical log Pow 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 persistence 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 Chemicals 
MEPC 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 Substances and Relevant Chemicals are all <3 which indicate that 

significant bioconcentration/bioaccumulation (<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/bioaccumulation will occur in aquatic 

organisms. Little biomagnification should occur 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 consortium including the World Health Organization 

and United Nations Environment Programme), and United Sates sources, such as the National 

Library of Medicine. In some cases, information from Material Safety Data Sheets were compiled. 

The studies discussed in these toxicology summaries represent 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 toxicity. 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/kg 

Dibromochloromethane 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/kg 
MEPC 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 irritation to the skin and eyes at 

sufficient concentrations. Where effects concentrations are provided, 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, 2004 
MEPC 59/2/11 

ANNEX 

Page 28 

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

Chemical Skin Eye Reference/Comments 

Dibromochloromethane Irritating to the skin Irritating to the eye Aldrich Chemical MSDS 

Bromoform Irritating to the skin Irritating to the eye Mallinkrodt Baker MSDS, 

2006 

Dichloroacetic 

acid 

Irritating to the skin 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 chemicals. These studies generally 

consider subchronic exposures, typically 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 day 

Dibromochloromethane 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 weights 

increased 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 studies are listed in Table 4.2.4-1. The studies are 

conducted in rodents over a period of 2 years. Some of the chemicals 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 provided, 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 mg/kg-day 

Mice Decrease in fertility 

in the high-dose 

groups. No lethal or 

teratogenic effects. 

IPCS, 2000 

Bromoform a. Gavage, doses up 

to 200 mg/kg on 

gestation days 6-15 

a. Rats a. Fetotoxic 

response, but no 

malformations. 

IPCS, 2000 

b. Gavage, doses up 

to 200 mg/kg 

for 105 days 

b. Mice b. No effect on 

fertility or 

offspring. 

Dichloroacetic 

acid 

a. Gavage, doses up 

to 125 mg/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 mg/kg-day 

Rats Body weight 

reduction and soft 

tissue malformation 

at higher doses 

IPCS, 2000 

Dibromoacetic 

acid 

Gavage, doses up 

to 250 mg/kg-day 

Rats Effects on male 

fertility 

IPCS, 2000 
MEPC 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 chemicals 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 potentially carcinogenic. Most of the 

chemicals are listed in IARC Group 3 ñ not classifiable as to carcinogenicity in humans. For 

most of these chemicals, there was inadequate evidence for cancer in humans and inadequate 

evidence in experimental animals. Chlororoform 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, 2000 
MEPC 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 details on the specific tests carried out, and the results of each of 

these tests. A wide range of results was observed for the different chemicals, 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, 2000 
MEPC 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 available information on uptake, absorption and excretion of the chemical. 

Most of the chemicals are excreted in the urine 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 chemicals metabolize into breakdown products, such as 

trichloroacetic acid and dichloroacetic acid, which 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, and dichloroacetic acid 

HSDB, 2008 

Chloramine 36Cl-Labelled chloramine is readily absorbed 

after oral administration 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, 2000 
MEPC 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 the 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 humans 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 toxicological 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 (biotic and abiotic) 

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 degradation 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% loss 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 found 
MEPC 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 degradation 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 coefficients (Pows) and bioaccumulation factors (BCFs) for the 

Active Substances and Relevant Chemicals are given above in section 4.1.5. The adsorption 

coefficients (Kocs) for the Active and Relevant Chemicals are given 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 freshwater 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 form free bromine which reacts with nitrogen to form bromamines 

which in turn form a number of bromo-organic, oxidation products, and Br-. The Relevant 

Chemicals listed in the above tables are the by-products expected 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 identified. The principal types of decay reactions 

which can ultimately react with organic matter are: 1) oxidation of amino-nitrogen (breakpoint 

reaction) which in turn react with organic matter; 2) oxidation of carbon; and 3) organic 

substitution. The most important decay reactions are probably those associated with the 

oxidation of amino-nitrogen which are important in the breakpoint phenomena of the chlorineammonia system. The breakpoint reactions are a function of chlorine dose, amino-nitrogen 

concentration, pH, temperature, and time of reaction. 

Trihalomethanes are unquestionably ubiquitous products of chlorination. Several variables can 

affect THM yields which include pH, temperature, chlorine dose, total organic carbon, and type 

of chlorine residual. Other factors being equal, higher pH tends 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 temperature affects the ultimate yield. Increasing chlorine dose increases 

yield up to point; however, several studies indicate that a plateau is reached. THM yields 

correlate positively with total organic carbon, but there 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. CO2 has been shown to be a major product of 

chlorination of natural estuarine water. Halocarbons 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 literature indicates (Helz, G.R. 1981) that only a 

few percent of the chlorine in typical doses is consumed in substitution reactions during the 

decay process. 

4.3.5 Potential physical effects on wildlife and benthic habitats 

No data were found that indicated the Active Substances 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 the 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 (discharge level), and treated water are presented in Table 4.4-1. 

Table 4.4-1: Physical and chemical properties 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 determined 
MEPC 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 concentration levels identified 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 confidential 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 Available 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 Analytical methods at environmentally relevant concentrations 

To date, Siemens has used two accredited environmental laboratories 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 performed internally either by Siemens personnel or subcontractors, 

such as NIOZ, trained by qualified Siemens chemists, using HACH spectrophotometer and the 

HACH reagent kits. 

The relevant analytical methods used for all Active Substances and Relevant Chemicals are listed 

in Table 4.5-1 and provided in the Appendix B. Appendix B also provides 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 USE OF THE ACTIVE SUBSTANCE (G9: 4.2.6) 

5.1 Manner of Application and Dosage 

The SiCURE system will treat ballast water on intake. 

SiCUREô BWMS is not based on a fixed Active Substance dose; it is based on variable dosing 

necessary to achieve a certain oxidizing power of the treated water - its ORP potential. The tests 

conducted in the laboratory settings using seawater from the North Sea off the Texel Island, 

the Netherlands show that this can be achieved with an HOCl dose not exceeding 6 mg/l, most 

likely within 2 to 6 mg/l range. The land-based and shipboard testing programme will show if the 

maximum concentration of 6 mg/l can be lowered 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 higher efficiency of the commercial size 40 micron weave screen 

filter in retention phytoplankton 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 flow control valves. Therefore, 

a typical dose range for disinfection will be between 2.0 and 5.5 mg/l, while a typical dose range 

for filterís biofouling control will be at 0.2 to 0.5 mg/l. 

Required chlorine dosing will be determined based on an ORP reading and controlled by PLC to 

reduce or increase DC current drawn from the transformer-rectifier to the electrochemical 

generator as necessary. 

5.2 Operational overview and process description 

Patent pending SiCUREô BWM system uses three major system components: 

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

phytoplankton; 

- an electrochemical generator that in-situ produces hypochlorous acid from seawater to 

provide disinfection of the filtered ballast water; and 

- an ORP control that regulates hypochlorous acid dose to meet biocide demand of the 

water being treated. 

Tests conducted by Siemens with cooperation from NIOZ have shown that a 50 micron filter 

could provide a complete removal of zooplankton. Removal of zooplankton is essential to 

reducing chlorine dose levels required for disinfection of the ballast water, thus minimizing 

potential risks of corrosion and 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 phytoplankton. 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 the electrochemical generator by using a 5.5 m3

/h 

(small capacity systems) or 11 m3

/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 direct (DC) current drawn 

through the electrochemical cell. Siemensí proprietary CHLOROPACÆ technology is used to 

generate HOCl. 

CHLOROPACÆ is well known in the maritime industry as it has been used for biofouling control 

of the main engine and auxiliary cooling water for over 30 years, with over 2,000 commercial 

and navy shipboard installations worldwide. It is known for its reliability 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 electrochemical produced by other manufacturers. It also employs 

Siemens proprietary anode coatings that allow producing HOCl in a wide range of seawater 

temperatures and salinities. There is no bulk storage of produced HOCl, it is injected into the 

ballast water main as soon as hydrogen gas had been 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, HOCl 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 CHLOROPACÆ is the heart of the SiCUREô BWMS, ORP control is its brain. Widely used 

in controlling disinfection of the recreational and cooling water, it is an ultimate and, 

importantly, low maintenance, analytical instrument measuring oxidizing power of water treated 

with HOCl or HOBr and practically 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 necessary to achieve a proper level of disinfection. 

The SiCUREô system is designed for shipboard applications for both new builds and retrofits. 

The system can be supplied as a skid mount or containerized, fully integrated package or as loose 

components. 

There will be no dry dock requirement 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 Retention time 

The tests show that employment of a 50 micron filter and an ORP controlled biocide treatment 

provides conditions when disinfection of the ballast water can be achieved within the very first 

day of treatment, most likely within a few hours. However, the retention time 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 environment. While this could be remedied by using 

a dechlorination step prior to the discharge, SiCUREô project team would like to avoid having 

any chemicals on board as this would present ship 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 point, at least till the land-based tests are completed, 

the retention time will stand at 5 days. 

Future tests will show if Active Substance residuals could be achieved at the environmentally 

safe levels in a shorter retention time, 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 Interface (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 start and stop of the ballast 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 degas 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 alarms 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 before 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 reading 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 include differential pressure setpoint (backwash 

trigger), differential pressure and backwash duration for the filter and ORP setpoint, ORP value, 

DC current, DC voltage, electrochemical generator flow, differential pressure 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 operation 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 logger and examine the data recorded. Look for any variation; 

and 

- monitor any abnormal alarm. 

5.5 System requirements 

Utility Requirements: The system requires 380-480 V, 3-phase 50/60 Hz AC power input, air 

(for failsafe valves) and small amount 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 provided as skid-mounted, fully enclosed in a 20-ft 

container or as loose components and installed either in an engine room, pump room or on a 

deck. A typical footprint of the skid-mount SiCUREô system to treat up to 1000 m3

/h will 

require about 4.2 m2

. Additional footprint is required for a filter. Its size will depend on a 

horizontal or vertical arrangement of the filter. For example, for up to 350 m3/h ballast water 

flow, filterís footprint will be of 1.55 m2

 for a vertical arrangement or 3.6 m2 for a horizontal 

arrangement. 

Personnel Requirements: The SiCUREô BWMS is designed to work in a fully automatic 

mode ñ there is no special personnel requirements for operating the system, rather then some 

limited preventive maintenance measure described below. 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 technical service and support specialists will ensure that a proper 

training and preventive maintenance are provided during regular port 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 

ChloropacÆ systems have been provided to major operators such as Bergesen, BP, Carnival, 

Leif Hoegh, Matson, Shell, Exxon Mobil, Statoil, Qatar Gas and Chevron. 

Many of those installations operating around the clock 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 solutions to maritime industry are vertically integrated; 

the key components of the system such as electrodes and anode coatings are manufactured 

directly by Siemens. 

5.7 System locations, considerations and limitations 

System Locations and Considerations: Based on Siemens experience with ChloropacÆ shipboard 

applications, it is expected that every installation will require engineering work together with a

shipowner, ship operator and a naval architect to determine the best location and piping 

configuration for the SiCUREô BWMS to provide for its safe operation. A location for each 

installation will have to be approved by a Classification Society. 

While electrochlorination part of the SiCUREô system 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 typically 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. SiCUREô 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 concentration of the generated biocides 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 SiCUREô 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 communicate with the shipsí central controls at the 

bridge. When connected the SiCUREô system operation can be monitored remotely at the bridge. 

When the system is started in automatic mode the Programmable 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 ready to operate, an alarm will signal and will be 

logged in the alarm list. The table below lists the systemís common faults 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 conditions 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 

Degassing See level instrument operating manual 

equipment high 

level fault b. Hypochlorite dosing pump See hypochlorite dosing pump operating 

manual 

Dosing a. Analyzer feed pump See pump operating manual 

Analyser fault b. ORP Analyzer instrument 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 pressure 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 the 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 clogging and is required to be bypassed, raw sea water will 

be the supply for the SiCUREô hypochlorite generator. 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 operation can commence. A separate 

strainer and a spare strainer basket are provided for the protection of the electrochlorination 

section of the system that will enable the user to finish ballasting. 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 shutting 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 storage 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 hydrogen gas. The system 

includes a degas tank with air blowers and hydrogen gas detecting instrumentation to ensure that 

the hydrogen gas has been safely diluted 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 catastrophic failure 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. 

5.9.3 Accidental release measures 

The SiCUREô system has the required alarms design to detect any possible 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 occurs, 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 all 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 chemicals 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 Substance in the sill will be similar to the ones that can be found in 

drinking water or swimming pool water. 

Respiratory Protection: None required under normal use conditions. Use NIOSH/MSHA 

approved organic vapour-acid-gas respirator with filter (qualified to wear respirator) during spill 

clean-up or other conditions that might produce irritating chlorine-like fumes. 

Skin Protection: Wear neoprene or rubber gloves and other protective clothing as appropriate to 

prevent skin contact. 

Eye Protection: Safety glasses with face shield or chemical goggles are recommended. 

Ventilation Protection: Use local exhaust 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 material 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 currently no recommended measures 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 emergency situations are limited to an adequate 

training by the ship management and Siemens personnel. The measures described in section 5.8 

are considered to be adequate to properly operate and manage the SiCUREô BWM system.

6 HAZARD CLASSIFICATION AND MATERIAL SAFETY DATA SHEETS

 (G9: 4.2.7) 

Hazard identification for Active Substances and Relevant Chemicals provided in Table 6-1 below 

is based on MSDS of commercially available products that contain referenced chemicals at 

significantly greater concentrations that produced by the SiCURE BWMS or could be found in 

the treated ballast water. Therefore the hazard identification presented in the Table 6-1 reflects 

potential hazards only and does not indicate any potential for exposure. 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 Active 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, bioaccumulation, and toxicity (G9: 5.1) 

7.1.1 Persistence (G9: 5.1.1.1) 

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. The 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 expected 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 toxic to fish (0.04 mg/L) and crustaceans (0.012 mg/L) based on a 

chronic NOEC criterion of <0.01 mg/L. The Active Substances may have the potential to be 
MEPC 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 shown in Table 4.1.2-1 for algae did not met OECD 201 

Guideline acceptability criteria but were included to provide an indication only of potential 

toxicity, further speculation regarding chronic toxicity of the Active Substances to algae is not 

warranted. No chronic toxicity data were found 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 available (bromate and two THMs) that these 

compounds are much less toxic than the Active Substances. 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 chloroform range from a low of 1.5 mg/L for fish up 

to 216 mg/L for algae. A 10 mg/L NOEC for algae exposed to bromoform is 3 orders of 

magnitude higher than the <0.01 mg/L level set for the Active Substances. No chronic data were 

found for dibromochloromethane. No acceptable OECD chronic data were found for any of the 

four HAAs under consideration for this dossier. 

The toxicity data are summarized below in section 7.1.4 as required 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 algae 
MEPC 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 applying for Basic Approval. The first goal of the 

testing was to test the SiCUREô BWMS control logic and to prove that all aquatic invasive 

species can be eliminated safely from the ballast water, prior to discharge. The second goal was 

to carefully evaluate the Active Substance residuals and disinfection by-products; results of this 

study will be presented in this section. 

Testing was carried out in collaboration with the 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 Oceanography 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 levels one may expect a 

high level of corrosion to the ballast water tank and high rate of DBP generation during the entire 

retention period. This is a typical example of overchlorination. As seen from Figure 7.2.1-3

(refer to confidential part of the 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 level 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 the NIOZ personnel using seawater collected from 

the North Sea, Texel harbour, in June to August (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 water 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. The data shown are an estimate based on an increased 

chlorine demand. ** One hour after treatment. 

As seen from the table, the highest 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 result in lower TRO and DBP levels. Therefore, a 

thorough toxicity testing programme is planned for land-based and 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 48
MEPC 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 water 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 that 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, residual concentration of Active Substance in ballast 

water, its decay rate, and evaluation of PEC, PNEC and their ratio. 

While the latter are addressed in the Risk Assessment section of the Dossier, this section will be 

dedicated to evaluation of the predicted decay rate of the Active Substance (TRO) under real life 

conditions. 

Decay rate of the halogen based TRO in seawater, and especially in industrial port water, is 

difficult to define as there are several factors affecting it in the real life scenario. Among these 

are chlorine demand, photolytic and heat decomposition processes. 

SWT has an extensive worldwide experience in providing chlorine based technical solutions for 

biofouling control of land-based power stations, offshore 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 between 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 between the amount of chlorine consumed in one 

contact period and that amount consumed in any other period. In general, this can be described as: 

D = k tn

Where: D = chlorine demand mg/l (chlorine 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 chlorine dose of 5.6 and 2.7 mg/l presented in 

Table 7.2.1-2 are presented in Tables 7.2.2-1 and 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 5.51
MEPC 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 derived from the plotted data: 

For a dose of 5.6 mg/l (high demand) Dt = 4.40 x t0.047 

For a dose of 2.7 mg/l (low demand) Dt = 1.92 x t0.058 

The derived models were used to calculate the halogen demand and the corresponding TRO 

levels to determine the half-life of the Active Substance in North Sea water off Texel Island. 

The results are presented in Figures 7.2.2-2 and 7.2.2-3. 

1

10

0.1 1 10 100 1000

Contact time, hours

Demand, mg/l

5.6 mg/l

2.7 mg/l

Figure 7.2.2-1: Halogen demand vs. contact 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 dose 
MEPC 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 lower 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 performed more frequently during 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 concentration 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 factor as low as 2, the half-life of TRO is 

less than 1 minute. With greater dilution rates it would be reasonable to assume that the half-life 

could be even lower. 

TRO in treated water TRO in the mix after certain time, mg/l 

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 0.03 
MEPC 59/2/11 

ANNEX 

Page 55 

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

7.3 Risk characterization and analysis (G9: 5.3) 

7.3.1 Reaction with organic matter (G9: 4.2.1.3) 

Major reactions of chlorine with organic matter in polluted water were described in section 4.3.4. 

The yield of THM and HAA identified as the major by-products of these reactions 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 concentrations in the treated water and, as a result, in the aquatic environment 

after discharge. On the other hand, the same reactions 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 reactions will also play a very important role of 

eliminating chlorine from the treated water being discharged into the port harbour. 

7.3.2 Characterization of degradation 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 regression analysis of the data using an exponential 

decay equation. 

The exponential decay equation predicts the dose level 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 section 7.2.2, the ìchlorine demandî half-life of TRO is: 

Chlorine Demandî Half-Life <1 second. 

According to the data in Fig. 7.3.2-1, during a holding period of from 24 to 120 hours the halflife of TRO due to a photolytic 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

R2 = 0.9704

0

1

2

3

4

5

6

0 20 40 60 80 100 120 140

Holding Time, hours

TRO, mg/l

Figure 7.3.2-1: Test data and exponential decay model 

7.3.3 Prediction of discharge and environmental 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. MAMPEC was originally programmed 

to calculate environmental concentrations of anti-fouling biocides released from ship coatings. 

In a modified way it can be used to calculate concentrations that are released constantly into the 

water by other processes like for example ballast water 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 necessary. These parameters define the harbour and its 

characteristics, the compound that is being released and the amount of ships and the amount of 

the specified compound released by those ships. This section provides 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 coefficient [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 therefore 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 possible to include the decay of the compound of 

interest during emptying the ballast water tank. In this case, therefore, a worst case scenario was 

assumed that the water released from the ballast tanks has the same concentration at the start and 

at the end of discharge. 

TRO concentrations in the ballast water 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 concentrations were used in calculations: 

- 0.13 mg/l - a concentration observed in treated water 120 hours after treatment; and 

- 0.55 mg/l - a concentration observed in treated water 24 hours 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 

time (TRO level).

It was assumed that there were 80 ships anchored in the Port of Rotterdam on an average day, 

discharging 397,000 (three hundred ninety thousand) m3

/day or about 16,540 m3/ 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 and 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 was 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 5.1117·107

 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 assumed 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 

number of ships in the harbour. The results of modeling are presented in Table 7.3.3-1,

Figures 7.3.3-1 and 7.3.3-2. 

The model simulation results show that the total amount of HOCl in port after discharge is 

mainly made up by the soluble fraction. The suspended fraction in all considered 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-01 
MEPC 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, h

TRO PEC, μg/l

average

minimum

maximum

Figure 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-life 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, h

TRO PEC, μg/l

average

minimum

maximum

Figure 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-life axe is in a logarithmic scale 

Predicted environmental concentrations of TRO (PEC TRO) based on the calculation with one ship 

vary significantly depending on which value of the TRO half-life was selected as a model parameter. 

For a half-life less than 4 hours and discharge concentrations between 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 between 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 concentration 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 approaches an asymptotic value. An asymptotic value of the predicted 

environmental TRO at infinite half-life (an assumption of no decay) can be directly associated 

with a dilution factor. Based on the data provided 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 PEC 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 water with the same holding time. It is expected 

that only about 10 ships in the port would actually be equipped with the SiCUREô system. 

Figure 7.3.3-3 presents the data for a half-life of 1 minute, Figure 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 half-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 harbor

PEC 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 harbor

PEC 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 minutes 
MEPC 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 harbor

PEC 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 environmental concentrations of TRO for the worst case 

scenario of 80 ships in the harbour are summarized in the Table 7.3.3.-2 below for the wide range 

of half-life values. 

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

TRO in Treated Water, Maximum PEC, μg/l at a Half-Life of 

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 concentrations of DBP for the worst case 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 

DBP PEC, μg/l 

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 < 0.7 
MEPC 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 using models other than MAMPEC that take into consideration 

the effect of a chlorine demand. These results will be used to define the SiCUREô BWMS 

environmentally safe holding time and will be provided for review in a documentation to be 

submitted for Final Approval. 

7.3.4 Assessment of potential for bioaccumulation (G9: 5.3.7) 

The risk of bioaccumulation in freshwater and saltwater pelagic organisms as well as epifaunal 

sediment organisms is low based on the log Pows of the Active 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 were <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 Substances and Relevant Chemicals through aquatic 

food webs, wildlife, and humans is low based on the log Pows and kocs. No data were found that 

suggest the Active Substances and Relevant Chemicals 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 chloroform 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 complete chronic database for (i.e., one or more of the three chronic 

trophic levels used in this dossier are not available), the acute toxicity database of the Relevant 

Chemicals provide additional data which may be used to access ecological risk to freshwater and 

saltwater organisms. Acute-to-chronic ratios (ACRs) have been 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 relationship between the responses 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 class. The maximum value for organics other than pesticides 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 are available to provide 

chronic NOECs, one may estimate potential risk for bromate, bromoform, and trichloroacetic acid. 

Bromate does not appear to be a risk to plants (8 mg/L) based on a chronic NOEC <0.01 mg/L 

under the worse case scenario given above. If one uses an acute-to-chronic ratio (ACR) of 27.5, 

the acute bromate data for fish and crustaceans have an estimated chronic NOEC >1.0 mg/L 

which suggests that bromate will not be toxic to any 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 estimate risk from ACRs are not available for the 

remainder of THMs and HAAs. 

One acute fish value (34 mg/L) is available for dibromochloromethane which indicates that this 

THM may have similar toxicity properties and risk potential as the other THMs in this dossier. 

Likewise, one acute fish value (106 mg/L) for dichloroacetic 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 conclusions regarding these HAAs. A great deal of 

uncertainty exists when one tries extrapolating risk 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 assessment factors given in Table 2 of The 

Methodology for the information gathering and the conduct of work of the GESAMP-BWWG 

(IMO, 2008b). 

Table 7.3.6-1: Predicted No-Effect Concentration (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 alga 
MEPC 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 Relevant 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 assessment with discharge toxicity 

TRO and DBP concentrations in the ballast water (see Table 7.2.1-2) five days after treatment 

exceed their corresponding PNECs (see Table 7.3.6-1). Based on the PNECs, the concentrations 

in the ballast tanks would be judged to be an ecological risk when discharged with no further 

decay and mixing in the receiving harbour. As discussed below in section 7.4; however, when 

the chlorinated ballast water is discharged and mixed 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 PEC/PNEC ratios using a 

worst case scenario. The lowest PNEC found in the risk characterization 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 ballast 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 average, 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 half-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/PNEC 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 holding 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 environment are indicated from the PEC/PNEC ratios 

when 10 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 HOCl held in the ballast water tanks for 120 hours and subsequently 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 Rotterdam at an average concentration of 0.55 mg/L 

with decay half-lives ranging from 0.0083 hours up to 3 hours. 

The following risks to the aquatic environment 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 for 120 hours and subsequently discharged into the 

Port of Rotterdam at an average concentration 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 initially chlorinated with 5.60 mg/L HOCl, held in the ballast water 

tanks for 24 hours and subsequently discharged at an average concentration of 0.55 mg/L into the 

Port of Rotterdam. 

As discussed in the risk characterization 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-02
MEPC 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 Relevant Chemicals will be below 1 taking into account 

dilution factor of 90 that were calculated for 80 ships discharging in the port of Rotterdam (see 

Table 7.3.3-3) and PNEC values listed in Table 7.3.6-1. Thus, it is expected 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 ships 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+00
MEPC 59/2/11 

ANNEX 

Page 68 

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

Table 7.4-4: DBP PEC/PNEC Ratios for Discharged Ballast Water 

in the Port of Rotterdam for 80 ships 

DBP PEC/PNEC 

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 Assessment is a method used to estimate the likelihood of adverse effects to human health

and the environment, based on toxicity and exposure information. The Risk Assessment section 

discusses potential risks to the safety of the ship, as well as potential exposures and risks to 

human populations who could potentially come into contact with ballast 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 water piping system is made via class approved 

automatic valves. In case of catastrophic failure 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 control 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 microbially 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 and 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 available database published by The Tanker Structure 

Cooperative Forum establishes corrosion rates of the untreated ballast 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 corrosion 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 estimate corrosion rates on an annual basis. 

For example in one report (BMT 2002), corrosion testing in seawater in presence of chlorine was 

performed in a special apparatus where electrically 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 days with chlorine being 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 were 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 (ballast 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 sediment). 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 adjusted 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 the wheel. This represents a 3-fold increase 

over the results reported by The Tanker Structure Cooperative Forum, which was a maximum 

corrosion rate of 1.2 mm/y. 

Based on this data, the report then makes an assumption on the basis of the operational scenario 

of a 30 day cycle ballast water treatment and that during that cycle the structure will be exposed 

to 2 days of high sodium hypochlorite dose and 4 days at a low dose (20% of total time) reducing 

chlorine levels to zero over time, the effective corrosion rate of bare exposed 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 chlorine will provide its major impact on corrosion 

rate of the pumps and pipes during the ballasting operations and the approach used in Ballast 

Water Evaluation report (BMT 2002) may not be correct 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 additions 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 grades were tested at chlorine 

concentrations of 0 (untreated seawater), 0.1 to 0.2 ppm and 1to 2 ppm. 

The first series of tests with electrically isolated pipes has shown 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 the free corrosion potentials have increased 

from -100 to 0 mV (vs. Standard Electrode (SCE)) to 300+/- 50 mV due to 

microbiologically induced corrosion (MIC); 

- 0.1 to 0.2 ppm ñ free corrosion potential has immediately stabilized at 300+/-50 mV 

(vs. SCE); and 

- 1 to 2 ppm ñ free corrosion potential has immediately stabilized at 560+/-60 mV 

(vs. SCE). 

Free corrosion potential of steel in 1 to 2 ppm chlorine 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 stainless steel tubes in seawater 

Day % of pipes with crevice corrosion 

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 propagation 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 of 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 corrosion of the ballast water tanks. Different 

studies show that MIC rate can be as high as 12 to 100 mm/y - well above the corrosion rate 

limits reported by The Tanker Structure Cooperative Forum. 

Assuming average MIC rate at 60 mm/y and the galvanic ratio presented 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 the corrosion rate observed in untreated seawater. 

This conclusion is also supported in other report that shows reduction in corrosion rates at 

low chlorine residuals. They also note that the 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 impact 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 water with high and low chlorine 

demand was treated to an ORP level 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 concentration of free chlorine in the treated 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 will have a minimal effect on corrosion of the ship materials. 

Moreover, if a duty cycle of chlorination is taken into the account, 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 treatment using SiCUREô BWM system. 

8.1.3 Fire/explosion 

As the SiCUREô system does not require the storage 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 hydrogen gas. The system 

includes a degas tank with air blowers and hydrogen gas detecting instrumentation to ensure that 

the hydrogen gas has been safely diluted 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 generation 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 cell or piping seal. The base area has spillage 

probes to alarm if water is present. These probes 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 high flow rate and pressure. For hydrogen to be 

released only as a gas would require very low flow and pressure to allow 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 must occur for release of hydrogen. Should an 

insignificant leak occur which does not provide sufficent water volume to be detected the small 

volume of diluted hydrogen is allowed to safely vent. 

8.2 Risk to human health

This section discusses potential exposure pathways 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 potential 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) related to the SiCUREô system include the Active 

Substances, which are hypochlorous acid, chloramine, hypobromous acid and bromamine, and 

Relevant Chemicals, which are chloroform, dibromochloromethane, bromoform, dichloroacetic 

acid, trichloroacetic acid, dibromoacetic acid, tribromoacetic acid and bromate. The Relevant 

Chemicals may be formed in small amounts as disinfection by-products. 

The Active Substances are produced in-situ and injected 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 complete 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 occur (such as ingestion or inhalation).

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

This section discusses potential human populations who could be exposed to COPCs in the 

ballast water. This section also 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 expected 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 safeties (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 and vented to a safe area. Leak detectors in the 

generator enclosure ensure 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 standard shipboard procedures for entering any 

tank/confined space, specifically 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 exposure to ballast water. A typical 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) assumes is ingested during swimming (which is 0.05 L/hr). It 

was also assumed that the technician could have exposure to the ballast water for 10 events over 

the course of a year, and that exposure would last no more than 1 hour per event. Therefore, 

these factors were used to modify drinking water guidelines, which assumed daily ingestion of 

water at a rate of 2L/day. The following modification factor was calculated: 

7,300 10days/yr

365days/yr

0.01liter/day event

2liter/day × =

This modification factor was used to modify drinking water guidelines developed by the World 

Health Organization (WHO, 2006) and USEPA (USEPA, 2006). The drinking water guidelines 

are derived to be protective of all potable uses of the water, including bathing, cooking, as well as 

consumption as drinking water. The comparison 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, there is little potential for accidental 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 little potential for exposure because of the low possibility of 

accidental release of sodium hypochlorite vapours and hydrogen gas. There is also little 

possibility for this group to be exposed directly 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 could 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 pathway 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 various chemicals were generally lower than their 

respective drinking water guidelines. Therefore, no adverse health effects would be expected 

from bathers exposed to diluted concentrations of these chemicals. 

Consumers of seafood 

Consumers of seafood from the harbour area where 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 exhibit 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 Kow (octanol-water partition coefficient) greater than 4 

(http://www.defra.gov.uk/ENVIRONMENT/chemicals/csf/criteria/detailed.htm). The COPCs 

evaluated here all have log Kows 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 COPCs 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 exposure. As discussed previously, there is little 

potential for exposure for the 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 skin, 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 adverse effects to the liver and kidney at the 

higher doses, and there are some reproductive effects generally at high doses (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 humans). 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 include inhalation exposure during accidental releases 

of sodium hypochlorite and hydrogen, and direct contact with ballast water. The possibility of 

inhalation exposure to sodium hypochlorite 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 groups 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 modify drinking water guidelines developed by WHO 

(WHO, 2006) and USEPA (USEPA, 2006). Table 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 developed by WHO and USEPA. Drinking water guidelines are based 
MEPC 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 volatiles in the household. As shown in Table 8.2.3-1, 

the concentrations of TRO (total oxidant, sum of hypochlorous acid and chloramines) and FAH 

are less than the drinking water guideline for hypochlorous acid. Amongst the detected 

chemicals, the only chemicals that slightly exceed the guidelines are bromate and total haloacetic 

acid (which only has a USEPA drinking water guideline). All of the other detected chemicals are 

less than the WHO and USEPA drinking 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 the ballast water several times over the course of 

the year, adverse health effects are not expected. 

It is possible, however, that there might be acute effects from occasional exposure. The USEPA 

(USEPA, 2006), has developed one-day drinking water health advisories for a child, that may be 

used to gain some idea of the potential for acute 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 the one-day health advisories. These results 

indicate that there is no potential for acute health risks based on exposure to ballast water. 

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

Risk-based Criteria Based 

on Likely Exposure Scenario

(e)

Chemical (mg/L)

TRO 0.55 5 (h) 4.0 (c)(h) No 29200 No

FAH 0.24 5 (h) 4.0 (c)(h) No 29200 No

Bromate 0.062 0.01 (j) 0.01 (c) Yes 73 No

TRO 0.13 5 (h) 4.0 (c)(h) No 29200 No

FAH 0.10 5 (h) 4.0 (c)(h) No 29200 No

Total THM 0.0406 NA 0.08 (c) No 584 No

 Trichloromethane ND 0.3 0.08 (d)(g)(l)(l) ND ND ND

 Tribromomethane 0.0387 0.1 0.08 (d)(g)(m)(l) No 584 No

 Bromodichloromethane ND 0.06 0.08 (d)(g) ND 438 ND

 Dibromochloromethane 0.0006 0.10 0.08 (d)(g) No 584 No

Total HAA 0.091 (i) NA 0.06 (c)(f) Yes 438 No

 Chloroacetic acid ND 0.02 (k) 0.06 (d)(f) ND 146 ND

 Dichloroacetic acid 0.0015 0.05 (j) 0.06 (d)(f) No 365 No

 Trichloroacetic acid ND 0.20 0.06 (d)(f) ND 438 ND

 Bromoacetic acid ND NA 0.06 (c)(f) ND 438 ND

 Dibromoacetic acid 0.038 NA 0.06 (c)(f) No 438 No

 Tribromoacetic acid 0.053 (i) NA NA No NA No

Notes:

FAH - Free available halogen (hypochlorous acid; no chloroamines).

HAA - Haloacetic acids.

NA - Not available; not analyzed.

ND - Not detected.

THM - Trihalomethanes.

TRO - Total oxidant (sum of hypochlorous acid and chloroamines).

(a) Treated North Sea water samples collected July and/or August 2008. Maximum concentration at specified day after treatment (i.e., at day 1 or day 5).

(b) World Health Organization (WHO), 2006. Guidelines for Drinking Water Quality, 3rd. Edition. 2006.

(c) United States Environmental Protection Agency. Office of Water. National Primary Drinking Water Maximum Contaminant Levels (MCLs). 2003.

(d) United States Environmental Protection Agency. 2006 Edition of the Drinking Water Standards and Health Advisories. 2006.

(e) Risk-based criteria calculated assuming an incidental ingestion rate of 0.01 L/day and an exposure frequency of 10 days/year. The lowest guideline value for each compound was 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) Value for five haloacetic acids (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid and dibromoacetic acid).

(g) Value for total trihalomethanes (chloroform, bromodichloromethane, dibromochloromethane and bromoform).

(h) Value for chlorine used (as a surrogate for hypochlorous acid).

(i) Tribromoacetic acid was not evaluated for this particular collection time; value shown is an estimate based on an increased chlorine demand.

(j) Provisional value.

(k) Value for monochloroacetic acid.

(l) Value under review.

Water Source 

Concentration 

Exceeds Risk-based 

Criteria?

Day after treatment: 1

Day after treatment: 5

USEPA Drinking Water Guidelines 

(c) (d)

(mg/L)

Water Source 

Concentration (a)

(mg/L)

WHO Drinking Water 

Guidelines (b)

(mg/L)

Water Source 

Concentration Exceeds

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 groups 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 for 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 treated 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 measured in tests of treated ballast water indicates 

that a technician would not experience adverse health 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 actual possibility of exposure is very low. 

8.3 Risks to the aquatic environment 

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 equipped 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 hour) PEC/PNEC ratios 

were calculated at less than 1.0 for the treated water with the holding time of 24 and 120 hours or more. 

When no chlorine demand is taken into account, (half-life times of greater than about 48 hours) 

PEC/PNEC ratios were calculated as greater than 1.0 for the treated water with the holding time 

of 24 and 120 hours. 

For one ship the PEC/PNEC ratios were calculated 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 shown 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 times for 80 ships in port. 

Use of a variable, on-demand chlorine dosing using 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 compounds 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 Overview of data and endpoints 

All of the chemicals were evaluated 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 toxic to fish (0.04 mg/L) and crustaceans (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 unacceptable OECD data when the chronic NOEC criterion 

of <0.01 mg/L is used. The chronic toxicity database shows for the Relevant Chemicals for 

which acceptable OECD chronic toxicity data are available (bromate and two THMs) that these 

compounds are much less toxic than the Active Substances. There are no studies indicating the 

possibility of endocrine disruption for any of these chemicals. 

The evaluation of mammalian toxicity involved assessing the chemicals for various endpoints, 

including acute and chronic toxicity, carcinogenicity, and developmental 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 concentrations than would be present in ballast 

water. The toxicity studies show that some of the COPCs result in adverse effects to the liver 

and kidney at the higher doses, and there are some reproductive effects generally at high doses. 

It is unlikely that people could be exposed to concentrations 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 measured concentrations were generally lower than 

their respective drinking water guidelines. Therefore, no adverse health effects would be 

expected from exposures that are much less than daily drinking water exposure. The low 

bioaccumulation potential for these chemicals indicates that consumers of seafood in the harbour 

areas would not face health risks from consuming seafood containing these chemicals. 

Therefore, the possibility of exposure health risks 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 guidelines. 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-protective guidelines for these chemicals. The potential risks to 

the safety of ships, human health and the environment are expected to be low because of the low 

potential for exposure. 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. Therefore, no chemicals are stored on board, thereby reducing 

the possibility of accidental release. There is little potential for exposure to ballast water. 

9.2 Test report data quality 

The test reports used in this application were from a variety of reputable sources, including the 

International Programme on Chemical Safety (a consortium of governmental bodies including 

the World Health Organization and the United Nations Environment Programme), the 
MEPC 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 agencies are valid and reproducible studies. The 

toxicology studies followed standard 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-Products in Aquatic 

Environments Annual Report Covering Period October 1, 1977 Through September 30, 1978. 

NUREG/CR-0504. U.S. Nuclear Regulatory 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 Disinfection to Freshwater 

Aquatic Life. EPA-600/3-75-012. U.S. Environmental Protection Agency, Duluth, MN. 

BMT Fleet Technology Ltd, 2002. Ballast Water 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 Meeting the Criteria for Listing as Causing Cancer via the 

Authoritative Bodies Mechanism: Dibromoacetic Acid. 

http://www.oehha.org/Prop65/CRNR_notices/admin_listing/intent_to_list/pdf_zip/NOIL_ABPkg

32a_dibromoacetic%20acid.pdf. 

Carlson, S., 1991. Fundamentals of Water Disinfection, Nuremberg, Germany. 

Cowgill, U.M., D.P. Milazzo, and B.D. Landenberger. (1989). Toxicity of Nine Benchmark 

Chemicals to Skeletonema costatum, a Marine Diatom. Environ. Toxicol. Chem. 8:451-455. 

Crecelius, E.A. 1979. Measurements of Oxidants 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. Toxicity Screening of Fifteen Chlorinated and 

Bromated Compounds Using Four Species of Marine Phytoplankton. Pages 307-310 in: Jolley, 

R.L. et al. (eds.). Water Chlorination Environmental 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.fishersci.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. Turley, and G.P. Ziegler. 1999. The Relative 

Acute Toxicity of Continuous and Intermittent Exposures of Chlorine 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 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. 

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 States 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 Chlorination 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 Experimental Streams. Pages 463-477 in: Jolley, R.L. et al. (eds.). Water 

Chlorination Environmental Impact and Health Effects, Vol. 6, Ann Arbor Sci., Ann Arbor , MI. 

Holland, G.A., J.E. Lasater, E.D. Newman, and 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. Handbook of Environmental Fate and Exposure Data for Organic 

Chemicals, Volume II Solvents. Lewis Publ., Chelsea, MI. 

Howard, P.H. (ed.). 1993. Handbook of Environmental Fate and 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 Research on Cancer. Chloroform. VOL.: 73 (1999). 

http://www.inchem.org/documents/iarc/vol73/73-05.html. 

IARC. 2004. International Agency for Research on Cancer. Chloramine. VOL.: 84 (2004) 

(p. 295). http://www.inchem.org/documents/iarc/vol84/84-02-chloramine.html. 

IMO (International Maritime Organization). 2008a. Marine Environment 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 Maritime 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 Maritime Organization, 

London, United Kingdom. 

IMO (International Maritime Organization). 2008d. Harmful Aquatic Organisms in Ballast 

Water. MEPC 58/2/7, GESAMP-BWWG 6/9, annex 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 Maritime Organization, 

London, United Kingdom. 

IPCS. 2000. International Programme on Chemical Safety. Environmental Health Criteria, 216. 

Disinfectants and disinfectant by-products. World Health Organization. 

http://www.inchem.org/documents/ehc/ehc/ehc216.htm#PartNumber:3. 

IPCS. 2004. International Programme on Chemical 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/documents/icsc/icsc/eics0868.htm. 

Kuhn, R. 1988. 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. 

Kuhn, R. and Pattard, M.. 1990. Data taken from ECOTOX Database (Last Update June 2008), 

United States Environmental Protection 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. Environmental 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 Organisms and Chemical Substances. Chemosphere 

36:115-127. 

LeBlanc, G.A. 1980. 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. 

Lund, E., Oxidative Inactivation of Poliovirus, Virological Laboratory of the Department of 

Bacteriology, University of Gothenburg, and the 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 Microcosms. Environ. Toxicol. Chem. 7:679-687. 

Rasmussen, V., Nissen, B., and Ebba Lund. A Comparison of Cryptosporidium, Giardia and 

Virus Inactivation Using Chlorine Residual and Redox Monitoring, Laboratory of Virology and 

Immunology, Dept. of Veterinary Microbiology, The Royal Veterinary and Agricaltural 

University, Copenhagen, Denmark, presented 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 relationship of ORP to PPM and Its 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 Brink (eds). 2008. Extrapolation Practice for 

Ecotoxicological Effect Characterization of Chemicals. CRC Press, Taylor & Francis Group, 

New York, NY. 

State of Michigan, Department of Environmental Quality, Surface Water Quality Division 

Ballast Water Treatment Evaluation Using Copper 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 Medicine. 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 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. 

U.S. Environmental Protection Agency. 1978. 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. 

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

USEPA. 1989. Risk Assessment Guidance for Superfund: Volume I. Human Health Evaluation 

Manual (Part A). Interim Final. Office of Emergency and Remedial Response. 

U.S. Environmental Protection Agency, 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/criteria/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 Hypochlorite. Draft Report. November 26, 2007. 

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

218-220. 

WHO. 2006. Guidelines to Drinking Water Quality. 3rd Edition. 2006. 

http://www.who.int/water_sanitation_health/dwq/gdwq3rev/en/. 

___________