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# E

MARINE ENVIRONMENT PROTECTION
COMMITTEE

61st session Agenda item 2 MEPC 61/2/9

28 March 2010 Original: ENGLISH

HARMFUL AQUATIC ORGANISMS IN BALLAST WATER

Application for Final Approval of the Severn Trent De Nora BalPure ®


### Ballast Water Management System

Submitted by Germany

SUMMARY

Executive summary: This document contains t he non-confidential information related to the application for Final Approval of the Severn Trent De Nora (STDN) BalPure ® 

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

Strategic direction: 7.1

High-level action: 7.1.2

Planned output: 7.1.2.5

Action to be taken: Paragraph 5

Related documents: BWM/CONF/36; MEPC 57/21; BWM.2/Circ.13 and BWM.2/Circ.24

Introduction

1 Regulation D-3.2 of the International Convention for the Control and Management of Ships' Ballast Water and Sediments 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 Procedure for approval of ballast water management systems that make use of Active Substances (G9) stipulates the required information (MEPC 57/21, annex 1, paragraph 4.2.1) and provisions for risk characterization and analysis (MEPC 57/21, annex 1, section 5), which, according to section 6 of Procedure (G9), should be evaluated by the Organization.

3 Basic Approval of the Severn Trent De Nora (STDN) BalPure ® 

### Ballast Water Management System was granted at MEPC 60.

### MEPC 61/2/9 Page 2

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### 4 The receiving competent authority in Germany has verified the application dossier and believes it to satisfy the data requirements of Procedure (G9) adopted by resolution MEPC.169(57). In accordance with BWM.2/Circ.24, Germany therefore submits the non-confidential part of the manufacturer's application dossier in the annex. The complete dossier will be made available to the experts of the GESAMP-BWWG with the understanding
of confidential treatment.

Action requested of the Committee

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

***

### MEPC 61/2/9 Annex, page 1

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### ANNEX

NON-CONFIDENTIAL INFORMATION ON THE SEVERN TRENT DE NORA BALPURE ®



### BALLAST WATER MANAGEMENT SYSTEM

CONTENTS

LIST OF ABBREVIATIONS

1 INTRODUCTION

1.1 Overview of the BalPure ® 

### technology 1.2 Response to the GESAMP-BWWG's comments on the application for Basic Approval

2 IDENTIFICATION OF THE ACTIVE SUBS TANCES AND RELEVANT CHEMICALS (G9: 4.1)

2.1 Introduction to the chemical basis of BalPure ® 

### Ballast Water Management System
2.2 Active Substances 2.2.1 Hypochlorous acid and hypobromous acid
2.3 Relevant Chemicals 2.3.1 Trihalomethanes (THMs) and haloacetic acids (HAAs) 2.3.2 2,4,6-Tribromophenol 2.3.3 Bromate, chlorate and monobromoacetonitrile 2.3.4 Hydrogen gas
2.4 Other chemicals
2.4.1 Sodium bisulfite and sodium bisulfate

3 DATA ON EFFECTS ON AQUATIC PLANTS, INVERTEBRATES AND FISH, AND OTHER BIOTA, INCLUDING SENSITIVE AND REPRESENTATIVE ORGANISMS (G9: 4.2.1.1)

3.1 Acute aquatic ecotoxicity 3.2 Chronic aquatic ecotoxicity 3.3 Endocrine disruption 3.4 Sediment toxicity 3.5 Bioavailability/biomagnification/bioconcentration 3.6 Food web/population effects

4 DATA ON MAMMALIAN TOXICITY (G9: 4.2.1.2)

4.1 Acute mammalian toxicity 4.2 Effects on skin and eye 4.3 Repeated-dose toxicity 4.4 Chronic mammalian toxicity 4.5 Developmental and reproductive toxicity 4.6 Carcinogenicity 4.7 Mutagenicity and genotoxicity
4.8 Toxicokinetics

### MEPC 61/2/9 Annex, page 2

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### 5 DATA ON ENVIRONMENTAL FATE AND EFFECT UNDER AEROBIC AND ANAEROBIC CONDITIONS (G9: 4.2.1.3)

5.1 Modes of degradation (biotic; abiotic) 5.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient
5.3 Persistence and identification of the main metabolites in the relevant media 5.4 Reaction with organic matter 5.5 Potential physical effects on wildlife and benthic habitats
5.6 Potential residues in seafood

6 PHYSICAL AND CHEMICAL PROPERTIES FOR THE ACTIVE SUBSTANCES, RELEVANT CHEMICALS, AND TREATED BALLAST WATER (G9: 4.2.1.4)

7 ANALYTICAL METHODS AT ENVIRONMENTALLY RELEVANT CONCENTRATIONS (G9: 4.2.1.5)

7.1 Analysis of Total Residual Oxidants (TRO as Cl 2 

### ) 7.2 Analysis of Disinfection By-products (DBPs)

8 USE OF ACTIVE SUBSTANCE

8.1 Manner of application 8.1.1 Process flow description 8.1.2 Chemical storage and handling 8.1.3 Various procedures and management measures

9 MATERIAL SAFETY DATA SHEETS (G9: 4.2.7)

10 RISK CHARACTERIZATION AND ANALYSIS

10.1 Screening for persistence, bioaccumulation, and toxicity (G9: 5.1) 10.1.1 Persistence (G9: 5.1.1.1) 10.1.2 Bioaccumulation (G9: 5.1.1.2) 10.1.3 Toxicity tests (G9: 5.1.2.3)

11 EVALUATION OF THE TREATED BALLAST WATER (G9: 5.2)

11.1 Total Residual Oxidants 11.2 Water quality parameters 11.3 Chemical analysis of disinfection by-products in treated ballast water 11.4 Ecotoxicity testing of treated ballast water, land-based testing 11.5 Determination of holding time 11.6 Reaction with organic matter 11.7 Characterization of degradation route and rate (G9: 5.3.5) 11.8 Prediction of Discharge and Environmental Concentrations (G9: 5.3.8) 11.8.1 Hydrodynamic modelling approach 11.8.2 Determination of substance concentrations and decay rates for modelling input 11.8.3 Predicted Environmental Concentration results from MAMPEC modelling 11.9 Effects on aquatic organisms 11.10 Assessment of potential for bioaccumulation
11.11 Effects on sediment
11.12 Effects assessment 11.13 Comparison of effect assessment with discharge toxicity

### MEPC 61/2/9 Annex, page 3

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### 12 RISK ASSESSMENT

12.1 Risk to safety of ship
12.1.1 Corrosion

12.2 Risks to human health

12.2.1 Introduction 12.2.2 Hazard identification/chemical of potential concern selection 12.2.3 Human Exposure Scenario
12.2.4 Health effects in humans

12.2.5 Risk characterization

12.2.6 Risk assessment conclusions 12.3 Risks to the aquatic environment

13 ASSESSMENT REPORT

14 REFERENCES

APPENDICES (provided in confidential dossier)

A.1 Key Data Table Summary A.2 Human Exposure Assessment
A.3 BalPure ® 

### Process Flow Diagram A.4 Material Safety Data Sheets/International Chemical Safety Cards A.5 Analytical Method Information A.6 Laboratory Quality Assurance Documents
A.7 Corrosion Information

LIST OF TABLES

Table 1 Overview of Chemical Identification Table 2 Acute Aquatic Ecotoxicity Data Table 3 Acute Aquatic Ecotoxicity Data – Land-based Testing Table 4 Overview of Chronic Aquatic Ecotoxicity Data Table 5 Chronic Aquatic Ecotoxicity Data – Land-based Testing
Table 6 Koc Values for Relevant Chemicals
Table 7 BCFs for Relevant Chemicals Table 8 Acute Mammalian Toxicity Data Table 9 Effects on Skin and Eye Table 10 Repeated-dose Toxicity Table 11 Chronic Mammalian Toxicity Table 12 Summary of Developmental and Reproductive Toxicity Data Table 13 Summary of Data on Carcinogenicity Table 14 Summary of Data on Mutagenicity and Genotoxicity Table 15 Summary of Uptake, Absorption, and Excretion of Chemicals Table 16 Fate and Mode of Degradation for Relevant Chemicals Table 17 Physical and Chemical Properties of Relevant Chemicals Table 18 Analytical Methods
Table 19 PBT Criteria Evaluation Table 20 Average Oxidant Values (mg/L) in Treated Ballast Water Table 21 Water Quality Data Table 22 Post-Treatment Disinfection By-product Concentrations – Day 1 Table 23 Post-Treatment Disinfection By-product Concentrations – Day 5 Table 24 Median Disinfection By-product Concentrations

### MEPC 61/2/9 Annex, page 4

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### Table 25 Summary of Relevant Chemical Concentration and Half-life for Modelling Table 26 PEC Summary for Environment A and Environment B Table 27 PNEC Derivation Summary
Table 28 PEC/PNEC Calculation for MAMPEC Environment A
Table 29 PEC/PNEC Calculation for MAMPEC Environment B Table 30 Comparison of Basic Approval and Land-based Ballast Water Residual COPC Exposure Point Concentrations Table 31 Summary of Dermal Intake Factors Table 32 Summary of Oral Intake Factors Table 33 Summary of Toxicity Criteria Table 34 Summary of Cancer Risks and Non-cancer Hazards for BalPure ® 

### Technicians Table 35 Summary of Cancer Risks and Non-cancer Hazards for BalPure ® 

### Technicians (or Others) – Ballast Water Discharge Sampling Table 36 Summary of Cancer Risks and Non-cancer Hazards for Ship's Crew/Dock

Workers Table 37 Summary of Cancer Risks for the General Public Table 38 Summary of Non-cancer Hazards for General Public
Table 39 Estimated Concentrations of THMs in Vent Air and Comparisons to PELs

LIST OF FIGURES

Figure 1 Overview of the BalPure ® 

### Ballasting Process Figure 2 Overview of the BalPure ® 

### Deballasting Process Figure 3 Conceptual Exposure Model, BalPure ® 

### System

### MEPC 61/2/9 Annex, page 5

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### LIST OF ABBREVIATIONS

Abbreviation Description Abbreviation Description

AIS Aquatic Invasive Species m Metres

BCAA Bromochloroacetic acid MBAA Monobromoacetic acid

BCF Bioconcentration Factor MCAA Monochloroacetic acid

B r 2 Bromine MEPC Marine Environment Protection Committee

BWMS Ballast Water Management System mV Millivolts

CAS Chemical Abstract Service μ g/L Micrograms per litre

Cl - Chloride ion MAMPEC Marine Antifoulant Model to Predict
Environmental Concentrations Cl 2 Chlorine

CO 2 Carbon dioxide m A Milliampere

CO Carbon monoxide μ M Micromolar

COPC Chemicals of Potential Concern mg/L Milligrams per litre

DBAA Dibromoacetic acid MSDS Material Safety Data Sheet

DBCAA Dibromochloroacetic acid NaHSO 3 Sodium bisulfite

DBCM Dibromochloromethane NaOCl Sodium hypochlorite

DBPs Disinfection By-products NIOZ Netherlands Institute for Sea Research

DC Direct Current NOAEL No Observed Adverse Effect Level

DCAA Dichloroacetic acid NOEC No Observed Effect Concentration

DCBM Dichlorobromomethane NOEL No Observed Effect Level (used interchangeably with NOAEL) DO Dissolved Oxygen

DOC Dissolved Organic Carbon OB r - Hypobromite ion

DPD N,N-diethyl-p-phenylenediamine OCl - Hypochlorite ion

EC 50 Effective concentration of
substance that causes 50% of maximum response OECD Organization for Economic Co-operation and Development

OIT Operator Interface Terminal

EDCs Endocrine Disrupting Chemicals ORP Oxidation Reduction Potential

EPC Exposure Point Concentrations PEC Predicted Environmental Concentrations

EPI Estimation Programs Interface PBT Persistence, Bioaccumulation, Toxicity

FAC Free Available Chlorine PFD Process Flow Diagram

FAB Free Available Bromine pKa Dissociation Constant

GESAMPBWWG Joint Group of Experts on the Scientific Aspects of Marine

Environmental Protection – Ballast Water Working Group PLC Programmable Logic Controller

PNEC Predicted No Effect Concentration

POC Particulate Organic Carbon

PPE Personal Protective Equipment

H + Hydrogen ion ppm Parts per million

H 2 Hydrogen gas PSU Practical Salinity Units

H 2 O 2 Hydrogen peroxide SAR Structure Activity Relationship

HSDB Hazardous Substances Data Bank SIDS Screening Information Data Set

HSO 3 Bisulfite ion STDN Severn Trent De Nora

HSO 4 Bisulfate ion TBAA Tribromoacetic acid

HAA Haloacetic acid 2,4,6-TBP 2,4,6-Tribromophenol

HOB r Hypobromous acid TCAA Trichloroacetic acid

HOCl Hypochlorous acid THM Trihalomethane

IARC International Agency for Research
on Cancer TOC Total Organic Carbon

TOXNET Toxicology Data Network

IMO International Mariti me Organization TRO Total Residual Oxidants

IUPAC International Union of Pure and Applied Chemistry TSS Total Suspended Solids

US EPA United States Environmental Protection Agency Koc Organic Carbon Partition
Coefficient

Kow Octanol/Water Partition Coefficient Kpa Kilopascal L/kg Litre per kilogram

LC 50 Lethal Concentration for 50% of test population

LD 50 Lethal Dose for 50% of test population

LEL Lower Explosive Limit

LOAEL Lowest Observable Adverse Effect

Level

### MEPC 61/2/9 Annex, page 6

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### 1 INTRODUCTION

Severn Trent De Nora, LLC (STDN) has developed the BalPure ® 

### Ballast Water Management System using seawater electrolysis combined with filtration and residual oxidant neutralization. STDN's experience with electr o-chlorination in a variety of industrial and maritime settings has proven the effectiveness of the technology. Testing of the system in the laboratory, during land-based testing and onboard ship has demonstrated the technology's effectiveness for disinfection of aquatic invasive species in ballast water.

Land-based testing of the BalPure ® 

### system was conducted at The Royal Netherlands Institute for Sea Research (NIOZ) during 2009. As required for Final Approval, an evaluation of aquatic ecotoxicity and Relevant Chemicals (e.g., disinfection by-products (DBPs)) was performed on samples drawn from the land-based test set-up. The quality assurance documents for the laboratories that performed ecotoxicity and DBP analyses are included in appendix A.6. Also presented are responses to comments of the GESAMP-BWWG (MEPC 60/2/16) during review of STDN's application dossier for Basic Approval (MEPC 60/2/9). STDN is submitting this application dossier to apply for Final Approval in accordance with Procedure (G9) (resolution MEPC.169(57)).

1.1 Overview of the BalPure ® 

### technology

The BalPure ® 

### system provides a safe and economical electrolytic process for the on-site generation of a biocide solution from seawater to disinfect aquatic invasive species (AIS) in ballast water. Ballast water treatment is accomplished using a simple three-step process of filtration, injection of a biocide solution, and residual oxidant neutralizat ion. The first phase is filtration using a 40 micron stainless steel mesh filter to remove organisms, large particles, and sediments. The second phase of the treatment process is electrochemical generation of the biocide solution. This involves passing a small supply (1/100 of total ballast flow) of seawater, either from the incoming ballast water line or sea cooling water, through electrolytic cells. The resulting disinfectant solution is injected directly into the incoming ballast water line where it will oxidize potential AIS. The third and final treatment process phase is residual oxidant neutralization to ens ure environmental acceptability. When the treated ballast water is ready to be discharged, sodium bisulfite is injected directly into the ballast water discharge line. The sodium bisulfite (oxidant neutralization) addition is controlled with ORP and metering pump technology.

The BalPure ® 

### system is designed to require minimal input from the ship's crew, with the system starting and stopping the necessary tr eatment steps based on electronic signals. This minimizes added duties to ship's crew and ensures proper ballast water treatment. More detailed information regarding operation of the BalPure ® 

### system is included in section 8.

1.2 Response to the GESAMP-BWWG's comments on the application for Basic Approval

Severn Trent De Nora submitted an application dossier for Basic Approval in August 2009 (MEPC 60/2/9). That dossier was reviewed du ring the 12th meeting of the GESAMP-BWWG in December 2009 and Basic Approval was recommended. The recommendations and comments by the GESAMP-BWWG (MEPC 60/2/16, annex 7), along with STDN's responses,

are summarized below:

.1 The Group recommended that a comprehensive evaluation of the corrosion impacts on ship's structures be conducted using the maximum anticipated treatment concentration, 20 mg/L (TRO as Cl 2 

### ) and that a realistic TRO decay profile may be considered if the total corrosion loss over the ship's

### MEPC 61/2/9 Annex, page 7

I:\MEPC\61\2-9.doc 

### life is to be projected. The Group noted however that such an analysis, while useful, is not necessary for the Group's consideration. The Group recommended that corrosion testing be conducted, and invited the applicant to consider the guidance provided in section 5.1 of the "Report of the eighth meeting of the GESAMP-BWWG", contained in document
MEPC 59/2/16.

Response: Additional information regarding corrosion is presented in section 12.1 "Risk to safety of ship". Further, STDN has initiated a detailed corrosion study as recommended by the Group. The results of the study will be considered as part of the Type Approval process with the German

Administration.

.2 The Group recommended to take into consideration the human exposure during sampling of ballast water at discharge (inhalation, dermal contact), as well as during periodic sediment cleaning (inhalation, dermal contact). These scenarios should also be considered in the conceptual exposure model (CEM).

Response: See section 12.2 "Risks to human health" for consideration of human exposure during sampling of ballast water at discharge and during periodic sediment cleaning.

.3 The Group recommended that the data sets on the analysis of Active Substance, Relevant Chemicals and Other Chemicals in treated ballast water should be further investigated during land-based and shipboard testing.

Response: STDN performed chemical analysis for Active Substances, Relevant Chemicals and Other Chemicals on samples drawn from the land-based test set-up. The human health risk assessment performed for Basic Approval has also been updated to reflect the land-based testing
results. See section 11 "Evaluation of the treated ballast water" and

section 12.2 "Risks to human health".

.4 The Group recommended that confirmation by further testing should be performed, that there will be no unacceptable risks (to ship safety, human health, or the environment) due to the chemical composition of the ballast water treated by this BWMS.

Response: See section 12.1 "Risk to safety of ship", section 12.2 "Risks to human health", and section 12.3 "Risks to the aquatic environment".

.5 The Group recommended that all missing information concerning the environmental exposure assessment using an appropriate model be provided.

Response: See section 11.8 "Prediction of discharge and environmental

concentrations".

.6 The Group recommended verification that the residual oxidant neutralization with sodium bisulfate on discharge is effective at all ballast discharges with MADC < 0.20 mg/L TRO as Cl 2



### .

Response: See section 11.1 "Total Residual Oxidants".

### MEPC 61/2/9 Annex, page 8

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### .7 The Group recommended that both acute and chronic ecotoxicity testing of treated ballast water be performed in accordance with the full requirements of Procedure (G9) at the maximum proposed treatment dose.

Response: As required by Procedure (G9), STDN performed ecotoxicity testing of treated/neutralized ballast water on samples drawn from the land-based test set-up. See sections 3.1 and 3.2 for Acute and chronic aquatic ecotoxicity data (Tables 3 and 5) and section 11.4 "Ecotoxicity testing of treated ballast water, land-based testing" for discussion of the results.

2 IDENTIFICATION OF THE ACTIVE SUBS TANCES AND RELEVANT CHEMICALS (G9: 4.1)

2.1 Introduction to the Chemical Basis of BalPure ® 

### Ballast Water Management System

The BalPure ® 

### system uses electrolysis of seawater to safely generate sodium hypochlorite on board, and immediately injects the solution directly into ballast water while it is pumped on board. Seawater is passed through electrolytic cells (electrolyzers) where it is subjected to medium amperage, low voltage direct current. Electrolytic cells are comprised of a cathode and an anode. At the outlet of the electrochemical generator, the seawater contains a mixture of chemicals produced at both the anode and cathode. Because seawater contains bromide ions, the electrochemical process results in the formation of hypochlorous acid (HOCl) in equilibrium with hypochlorite ion (OCl
- 

### ), hypobromous acid (HOBr) in equilibrium with hypobromite ion (OBr
- 

### ), and hydrogen gas (H 2 

### ) as a by-product. During the electro-chemical process a small amount of caustic (OH
- 

### ) is also produced, which is effectively neutralized within the cell and causes no apparent increase in the pH of treated ballast water.

The measurable oxidant species present during chlorine-based water disinfection, and the terminology used, is often a point of confusion. By industry standards and convention, all chlorine present in a water sample, regardless of form, is referred to as Free Available Chlorine (FAC). FAC includes Cl 2 

### , HOCl, and OCl
- 

### . When including chloramines, the term Combined (or Total) Chlorine is used. Similarly, all bromine species present in a water sample are referred to Free Available Bromine (FAB). When including bromamine the term Combined (or Total) Bromine is used. The common factor in all of these chemical species is that they are considered oxidants, and due to the difficulty in measuring each chemical species individually in a complex water sample, the term Total Residual Oxidants (TRO) is used to include all of these oxidants when present in a sample. To clarify:

Free Available Chlorine (FAC) = Cl 2 

### + HOCl + OCl
- 

### Combined (or Total) Chlorine = FAC + chloramine Free Available Bromine (FAB) = Br 2 

### + HOBr + OBr
- 

### Combined (or Total) Bromine = FAB + bromamine Total Residual Oxidants (TRO) = FAC + chloramine + FAB + bromamine

Therefore, in this dossier, TRO is used to descr ibe the total of all oxidants present in treated water. The chemical methods used for analyzing TRO often state that the measurement is calculated as mg Cl 2 

### /L. However, these methods include all of the oxidants present in a water sample as mentioned above, not just Cl 2



### .

Severn Trent De Nora classifies the substances associated with the BalPure ® 

### system using the definitions of Active Substances, Re levant Chemicals, and Other Components as provided in Procedure (G9) Methodology (23 May 2008) and presents information on each in

the sections below.

### MEPC 61/2/9 Annex, page 9

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### 2.2 Active Substances

2.2.1 Hypochlorous acid and hypobromous acid

To avoid storing Active Substances on board, the BalPure ® 

### system safely generates sodium hypochlorite by electrolysis of seawater. Se awater is passed through electrolytic cells (electrolyzers) where it is subjected to medium amperage, low voltage direct current. The electrolytic solution generated by the BalPure ® 

### system will consist of a near equal mixture of hypochlorous acid (HOCl) and hypochlorite ion (OCl
- 

### ) at the pH of seawater (typical range of 7.5-8.4). As discussed above in section 2.1, the combination of Cl 2 

### , HOCl, and OCl
- 

### is commonly referred to as free available chlorine (FAC).

Because seawater also contains bromide ion, it is important to note that reactions similar to those occurring with chloride ion can also be occurring with bromide ion in the electrolytic cell. For example, bromide ion will form Br 2 

### . At the pH of seawater the electrolytic solution generated by the BalPure ® 

### system will also consist of a mixture of hypobromous acid (HOBr) and hypobromite ion (OBr
- 

### ), with a slightly greater proportion of the mixture existing as HOBr. As discussed in section 2.1, the combination of Br 2 

### , HOBr, and OBr
- 

### are commonly referred to as free available bromine (FAB).

In the solution generated, hypochlorous acid (HOCl) in equilibrium with hypochlorite ion (OCl
- 

### ) and hypobromous acid (HOBr) in equilibrium with hypobromite ion (OBr-) are the actual disinfecting agents. In this dossier, these Active Substances are considered together and referenced as Total Residual Oxidants (TRO as Cl 2 

### ).

Details on the primary cell reactions occurring in the electro-chemical generation process in seawater and the effect of pH on the distribution of chemical species formed were presented in STDN's application dossier for Basic Approval (MEPC 60/2/9, section 2.2.1).

2.3 Relevant Chemicals

Disinfection of water with chlorine-based disinfectants can result in the formation of disinfection by-products (DBPs). Due to t he neutralization step, the Relevant Chemical sodium bisulfite may also be present in ballast water discharge. Data on the substances that had been analysed during initial pilot studies were presented in STDN's application dossier for Basic Approval (MEPC 60/2/9). During land-based testing of the BalPure ® 

### system at NIOZ the same substances, along with additional DBPs were evaluated. The substances that were analysed for and presented in the Basic Approval dossier, and the substances evaluated for Final Approval are summarized in the columns below. Substances denoted with an "*" are those with a measurable concentration in samples from land-based testing.
Substances with a measurable concentration in treated/neutralized ballast water are presented in this dossier. Substances with no measurable concentration (e.g., chlorate, bromate) are not considered further in this dossier.

Basic Approval Final Approval

THMs THMs

Chloroform Chloroform
Bromoform Bromoform*
Dibromochloromethane Dibromochloromethane*
Dichlorobromomethane Dichlorobromomethane*

### MEPC 61/2/9 Annex, page 10

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### HAAs HAAs

Monochloroacetic acid Monochloroacetic acid*
Dichloroacetic acid Dichloroacetic acid*

Trichloroacetic acid Trichloroacetic acid
Monobromoacetic acid Monobromoacetic acid*
Dibromoacetic acid Dibromoacetic acid*
Bromochloroacetic acid Tribromoacetic acid*
Bromochloroacetic acid*
Dibromochloroacetic acid*

Dichlorobromoacetic acid

Other Substances Other Substances

Bromate 2,4,6-Tribromophenol*

Monobromoacetonitrile
Chlorate

Bromate
Sodium Bisulfite*
Sodium Bisulfate*

For the treated/neutralized ballast water samples evaluated during land-based testing, chemical analysis was performed by Eurofi ns/Analytico (The Netherlands) and NovaChem Laboratories (USA). The Relevant Chemicals are discussed in more detail in the following

sections.

Additionally, during the electrolysis process hydrogen gas is produced. For this reason, hydrogen gas is considered as a Relevant C hemical and is discussed in more detail in
section 2.3.4.

Table 1 provides a summary of the substances potentially associated with the BalPure ®


### system.

Table 1: Overview of Chemical Identification

Substance (IUPAC Name) Identification

Numbers Chemical

Formula Structural

Formula Molecular Weight Dose/Classification

in Treated Ballast

Water

Active Substances in Ballast Water

Hypochlorous acid (Sodium Hypochlorite) CAS # 7681-

52-9 HOCl 52.46 <15 mg/L TRO as Cl 2

Hypobromous acid (Sodium Hypobromite) CAS # 13824-

96-9 HOBr 96.91 <15 mg/L TRO as Cl 2

Relevant Chemicals

Bromate (as sodium bromate) CAS # 7789-

38-0 NaBrO 3 150.89 By-product

Chlorate CAS # 14866-

68-3 ClO 3 - 83.451 By-product

Hydrogen CAS # 133-74-

0 H 2 H---H 2.016 By-product

Monobromoacetonitrile CAS # 590-17-

0 C 2 H 2 BrN 119.947 By-product

### MEPC 61/2/9 Annex, page 11

I:\MEPC\61\2-9.doc Substance (IUPAC Name) Identification

Numbers Chemical

Formula Structural

Formula Molecular Weight Dose/Classification

in Treated Ballast

Water

2,4,6-Tribromophenol CAS # 118-79-

6 C 6 H 3 Br 3 O 330.80 By-product

THMs

Dibromochloromethane CAS # 124-48-

1 CHBr 2 Cl 208.29 By-product

Dichlorobromomethane CAS # 75-27-4 CHBrCl 2 163.8 By-product

Tribromomethane (bromoform) CAS # 75-25-2 CHBr 3 252.77 By-product

Trichloromethane (chloroform) CAS # 67-66-3 CHCl 3 119.38 By-product

HAAs

Bromochloroacetic acid CAS # 5589-

96-8 C 2 H 2 BrClO 2 173.39 By-product

Monochloroacetic acid CAS # 79-11-8 C 2 H 3 ClO 2 94.50 By-product

Dibromoacetic acid CAS # 631-64-

1 Br2CHCOOH 217.84 By-product

Dichloroacetic acid CAS # 79-43-6 CHCl 2 COOH 128.9 By-product

Dibromochloroacetic

acid CAS # 5278-

95-5 C 2 HBr 2 ClO 2 252.29 By-product

Dichlorobromoacetic
acid CAS # 71133-

14-7 C 2 HBrCl 2 O 2 207.84 By-product

Trichloroacetic acid CAS # 76-03-9 CCl 3 COOH 163.4 By-product

Tribromoacetic acid CAS # 75-96-7 C 2 HBr 3 O 2 296.74 By-product

Monobromoacetic acid CAS # 79-08-3 C 2 H 3 BrO 2 138.95 By-product

### MEPC 61/2/9 Annex, page 12

I:\MEPC\61\2-9.doc Substance (IUPAC Name) Identification

Numbers Chemical

Formula Structural

Formula Molecular Weight Dose/Classification

in Treated Ballast

Water

Other Chemicals

Sodium Bisulfate CAS # 7681-

38-1 HNaO 4 S 120.06 By-product

Sodium Bisulfite CAS # 7631-

90-5 NaHSO 3 104.06 Neutralizing agent



### 2.3.1 Trihalomethanes (THMs) and haloacetic acids (HAAs)

During the disinfection process, reactions with organic materials present in water may result in
the formation of THMs and HAAs. The amount of THMs and/or HAAs formed as DBPs will vary depending on water quality. The following THMs had measurable concentrations in
treated ballast water from the land-based te st set-up: dichlorobromomethane (DCBM), dibromochloromethane (DBCM), and bromoform. The data is presented in section 11.3, Tables 22 and 23. Bromoform was also present at low levels in untreated (control) water, and has been documented to occur naturally in seawater as it is produced by various algal species (HSDB/TOXNET Tribromomethane, 2009; Goodwin et al., 1997; Ohsawa et al. , 2001).

The following HAAs had measurable concentrations in treated ballast water from the land-based test set-up: bromochloroacetic ac id (BCAA), monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), monobromoacet ic acid (MBAA), dibromochloroacetic acid (DBCAA), tribromoacetic acid (TBAA), and dibromoacetic acid (DBAA). The data is presented in section 11.3, Tables 22 and 23.

2.3.2 2,4,6-Tribromophenol

2,4,6-Tribromophenol (TBP) did not have measurable concentrations (<0.1 μg/L detection limit) in ballast water discharge from the high salinity test cycles. 2,4,6-TBP was detected at low levels (maximum = 1.3 μg/L) in ballast water discharge from the low salinity test cycles (section 11.3, Tables 22 and 23). 2,4,6-TBP was also detected in the untreated (control) samples at the same, or higher, concentrations. 2,4,6-TBP has been documented to occur in natural environments, either as a pollut ant from anthropogenic sources (wood industry, antifungal use) or from natural production by marine benthic organisms (OECD SIDS, 2003).

As presented in Table 4 below, the lowest chronic effect concentration identified for 2,4,6-TBP is 0.10 mg/L ( Daphnia magna ). The 2,4,6-TBP concentration measured in ballast water discharge is well below this effect concentration in both high and low salinity test waters. Therefore, 2,4,6-TBP is not considered to be present at concentrations of environmental concern in ballast water discharge. However, because 2,4,6-TBP did have measurable concentrations in the low salinity tests, data to allow for a full risk assessment is included in this dossier. 2,4,6-TBP was also included in the hydrodynamic modelling evaluation to verify low potential aquatic environmental risk.

2.3.3 Bromate, chlorate and monobromoacetonitrile

The presence of bromate ions in treated ballast water was evaluated during land-based testing at NIOZ and concentrations were not measurable (<10 μg/L detection limit) (Tables 22 and 23). Further, the lowest acute aquatic toxicity effect concentration located for bromate is 13.6 mg/L ( Glenodinium halli ) and the lowest chronic effect concentration located

### MEPC 61/2/9 Annex, page 13

I:\MEPC\61\2-9.doc 

### is 16 mg/L ( Thalassiosira pseudonana ) (Tables 2 and 4, respectively). As bromate in ballast water discharge is non-detectable and well below these effect concentrations, it is not present at environmentally relevant concentra tions. As such, bromate was not included in the hydrodynamic modelling assessment and furt her data on bromate are not considered in this dossier for Final Approval.

Chlorate was not an anticipated DBP but was analysed for verification. Samples from the land-based test set-up demonstrated that chlorate was not present in ballast water discharge in measurable concentrations (<50 μg/L detection limit) (Tables 22 and 23). Therefore,
chlorate is not addressed further in this dossier.

Monobromoacetonitrile was also a DBP evaluated in ballast water discharge samples from the land-based test set-up at NIOZ. Concentrations in both low and high salinity test cycles were not measurable (<1.0 μg/L or <10.0 μg/L detection limits). Therefore, monobromoacetonitrile is
not addressed further in this dossier.

2.3.4 Hydrogen gas

Hydrogen (H 2 

### ) is formed as a by-product of seawater electrolysis. Due to the explosive properties of hydrogen gas, allowing it to accumulate in the ballast tanks would create an unsafe situation. Therefore, the hydrogen produced during the electro-chlorination process is separated immediately upon exiting from the electrolytic cell using a patented cyclone separation device and is not allowed to enter the ballast water piping. The separated hydrogen gas is diluted to less than 1% hydrogen by forced air blowers and vented to the atmosphere outside of the ship. The lower explosive limit (LEL) for hydrogen is 4% and the operating limitations of the system provide a four-fold safety factor.

Relevant information pertaining to potential risks associated with hydrogen gas was provided in STDN's application dossier for Basic A pproval (MEPC 60/2/9). The GESAMP-BWWG considered the assessment and safety measures presented in Basic Approval with regard to

H 2 

### acceptable (MEPC 60/2/16, annex 7, sections 3.2.5 and 3.3.2).

2.4 Other chemicals

2.4.1 Sodium bisulfite and sodium bisulfate

During discharge of treated water (deballasting), sodium bisulfite (NaHSO3) is injected into the ballast water discharge line to neutralize residual oxidants that may be present. The bisulfite chemically reduces any free chlorine and/or hypochlorous acid to chloride ion, and any free bromine and/or hypobromous acid to bromide ion. During land-based testing the highest residual sodium bisulfite concentration measured in the whole effluent after injection was 8.0 mg/L. Since the lowest sodium bisulfite LC 50 

### located was 81 mg/L ( Daphnia magna ) (Table 2), which is significantly higher than the highest residual sodium bisulfite measured in ballast water discharge (8.0 mg/L), aquatic environmental risks would not be expected. Further, sodium bisulfite does not bioaccumulate, is highly soluble in water, and not expected to adsorb to sediments. However, to ensure that sodium bisulfite that may be present in neutralized discharge does not present environmental risk, data to allow for a full risk assessment was presented in STDN's application dossier for Basic Approval (MEPC 60/2/9) and is evaluated further in this Final Approval dossier. Sodium bisulfite was also included in the hydrodynamic modelling evaluation.

When sodium bisulfite reduces the chlorine and/or bromine species present as residual oxidants in treated water, bisulfate ion can be formed. Bisulfate ion dissociates into sulfate and hydrogen ions. Because the pKa for the bisulfate ion/sulfate ion equilibrium is approximately 2,

### MEPC 61/2/9 Annex, page 14

I:\MEPC\61\2-9.doc 

### bisulfate ion that is formed during the neutralization step is expected to be in the form of sulfate ion. Natural seawater typically contains approximately 3 g/L (3,000 mg/L) of sulfate ion.

Sodium bisulfate (as sulfate ion) was measured in samples collected from the land-based test set-up to verify that the neutralizing agent does not cause a significant increase in the level of sulfate ion present. The data show that the concentrations of sulfate ion in neutralized ballast water compared to untreated (control) water is not significantly different. The data are presented in section 11.3, Tables 22 and 23. Sulfate is not considered to pose unacceptable environmental risks and is not evaluated further in this dossier. Based on the GESAMP-BWWG report (section 3.1.1.4), this approach is accepted by the Group.

3 DATA ON EFFECTS ON AQUATIC PLANTS, INVERTEBRATES AND FISH, AND OTHER BIOTA, INCLUDING SENSITIVE AND REPRESENTATIVE ORGANISMS (G9: 4.2.1.1)

A literature search was conducted to locate existing aquatic ecotoxicity data for the

substances associated with the BalPure ® 

### system. The data summarized in Tables 2 and 4 present the acute and chronic toxicity data that was identified. A complete base-set for fish, crustaceans, and algae was not located for all substances and in some cases the data do not meet validity criteria. However, the data has been provided as supporting information and is discussed in relation to the Predicted No Effect Concentration (PNEC) derivation in

section 11.9.

Tables 3 and 5 summarize acute and chronic ecotoxicity data on whole effluent from land-based testing studies of the BalPure ® 

### system. Toxicity testing was done in conjunction with studies performed at the Royal Netherlands Institute for Sea Research (NIOZ), Texel (the Netherlands). Toxicity testing was performed by Grontmij/AquaSense (the Netherlands) and Chemex Environmental International Ltd. (UK). Toxicity tests were conducted with six taxonomic groups including bacteria, algae, crustaceans, rotifers, mollusks and fish in two water types, i.e. brackish water (low salinity) and marine water (high salinity). The samples for ecotoxicity testing were collected directly from the discharge pipe on Day 1 and on Day 5 after ballast water treatment and neutralization. Samples for analysis were stored in proper sample containers at 4°C and transported to the designated laboratory within 24 hours of collection. Analysis of the samples occurred within the time specified under standard laboratory procedures. All tests were performed according to laboratory protocols based on internationally recognized ISO, OECD, AS TM, and Parcom/OSPAR guidelines. Further, water quality data from the land-based test cycles at NIOZ are presented in section 11.2 "Evaluation of treated ballast water (Table 21)".

3.1 Acute aquatic ecotoxicity

The following table summarizes the data found in literature concerning acute aquatic ecotoxicity for the substances associated with the BalPure ® 

### system. In some cases, data could not be located for all three taxonomic groups (fish, crustaceans and algae). Literature concerning acute aquatic toxicity for bromochlor oacetic acid, dibromochloroacetic acid, and tribromoacetic acid could not be located for fish, crustaceans or algae. Similar data gaps are noted in other dossiers submitted for approval under Procedure (G9), suggesting that other literature searches have had similar findings. However, when available, data for other taxonomic groups (amphibians and ciliates) or alternative endpoints (LC 100 

### or EC 03 

### ) are included as supporting information.

To complete the data set for sodium bisulfite, STDN commissioned a 96-hour growth study with
Skeletonema costatum (Nautilus Environmental, 2009) that investigated potential toxic effects for several concentrations of sodium bisulfite. The study resulted in an EC 50 

### of 224 mg/L.

### MEPC 61/2/9 Annex, page 15

I:\MEPC\61\2-9.doc 

### Table 2: Acute Aquatic Ecotoxicity Data

Substance F
C

A

Am Ci Species Test Type E(L)C 50 mg/L NOEC mg/L Reference/
Comments

TRO as Cl 2 (Fresh water) F Oncorhynchus mykiss 15-d survival 0.059 N/A Fisher et al. (1999)

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

A Natural phytoplankton 47-h change in Chl a <0.1 N/A Brooks and Liptak (1978)

TRO as Cl 2 (Saltwater) F Menidia beryllina 96-h survival 0.143 N/A Fisher et al. (1999)

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

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

Hypochlorous
acid F Oncorhynchus mykiss 96-h survival 0.032 N/A US EPA ECOTOX (Thatcher, 1978)

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

A Porphyra yezoensis 10-d growth 1.4 N/A US EPA ECOTOX (Maruyama et al., 1988)

A Porphyra yezoensis 10-d mortality 2.3 N/A US EPA ECOTOX (Maruyama et al., 1988) Hypobromous
acid A Chlorella sorokiniana 18-h survival 1 N/A US EPA ECOTOX (Kott and Edlis, 1969)

Relevant Chemicals

Bromate F Morone saxatilis 96-h survival 30.8 N/A Richardson et al. (1981)

C Neomysis
awatschensis 24-h survival 176 N/A US EPA ECOTOX (Crecelius, 1979)

A Glenodinium halli Cell growth; exposure period not specified 13.6 N/A Hutchinson et al. (1997)

2,4,6- Tribromophenol F Oryzias latipes 96-h survival 1.5 N/A OECD SIDS (2003)

F Pimephales promelas 96-h survival 6.25 N/A OECD SIDS (2003)

F Cyprinus carpio 96-h survival 1.1 N/A OECD SIDS (2003)

C Daphnia magna 48-h immobilization 2.2 N/A OECD SIDS (2003)

C Daphnia magna 48-h immobilization 0.26 N/A OECD SIDS (2003)

A Selenastrum capricornutum 72-h biomass 0.76 N/A OECD SIDS (2003)

A Selenastrum capricornutum 24-48-h growth 1.1 N/A OECD SIDS (2003)

A Selenastrum capricornutum 24-72-h growth 1.6 N/A OECD SIDS (2003)

THMs

Chloroform F Lepomis macrochirus 96-h survival 14 N/A US EPA ECOTOX (Anderson and Lusty, 1980)

F Cyprinus carpio 72-120-h egg
fertilization to hatch 97 N/A Mattice et al. (1981)

C Artemia salina 24-h survival 30 N/A US EPA ECOTOX (Foster and Tullis, 1984)

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

Bromoform F Cyprinodon variegates 72-h survival 18 N/A US EPA ECOTOX (Heitmueller et al., 1981)

F Cyprinus carpio 72-120-h egg
fertilization to hatch 52.3 N/A Mattice et al. (1981)

C Daphnia magna 48-h immobilization 46 N/A US EPA ECOTOX (LeBlanc, 1980)

A Skeletonema

costatum 96-h growth

inhibition 12.3 N/A US EPA ECOTOX (1978)

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

Ci Tetrahymena pyriformis 24-h growth 650 N/A US EPA ECOTOX (Yoshioka et al., 1985)

### MEPC 61/2/9 Annex, page 16

I:\MEPC\61\2-9.doc

Substance F
C

A

Am Ci Species Test Type E(L)C 50 mg/L NOEC mg/L Reference/
Comments

Dichlorobromomethane F Oryzias latipes 96 h survival 72 N/A Toussaint et al. (2001)

F Cyprinus carpio 72-120-h egg
fertilization to hatch 67.4 N/A Mattice et al. (1981)

Ci Tetrahymena pyriformis 24-h growth 240 N/A US EPA ECOTOX (Yoshioka et al., 1985)

HAAs

Dichloroacetic

acid C Daphnia magna 24-h immobilization 106 N/A US EPA ECOTOX (Trenel and Kuhn, 1982)

C Nitocra spinipes 96-h survival 23 N/A US EPA ECOTOX (Linden et al, 1979)

Am Xenopus laevis 96-h development 3560 N/A US EPA ECOTOX (Fort et al., 1993)

Trichloroacetic

acid F Pimephales promelas 96-h survival 2000 N/A US EPA ECOTOX (Dennis et al., 1979)

C Daphnia magna 48-h immobilization 2000 N/A US EPA ECOTOX (Dennis et al., 1979)

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

Dibromoacetic
acid F Pimephales promelas 24-h survival 160 N/A US EPA ECOTOX (Mayes et al. , 1985)

F Pimephales promelas 48-h survival 107 N/A US EPA ECOTOX (Mayes et al. , 1985)

F Pimephales promelas 72-h survival 81 N/A US EPA ECOTOX (Mayes et al. , 1985)

F Pimephales promelas 96-h survival 69 N/A US EPA ECOTOX (Mayes et al. , 1985)

Dibromochloroacetic acid No data found in literature

Tribromoacetic

acid No data found in literature

Bromochloroacetic acid No data found in literature

Monobromoacetic acid F Cyprinus carpio 5-h survival 222 N/A US EPA ECOTOX (Loeb and Kelly, 1963)

C Daphnia magna 24-h survival 34 N/A US EPA ECOTOX (Kuhn, 1988)

A Scenedesmus subspicatus 48-h survival 0.34 N/A Kuhn and Pattard (1990)

Monochloroacetic acid F Cyprinus carpio 28-h survival 191 (LC100) N/A US EPA ECOTOX (Loeb and Kelly, 1963)

C Daphnia magna 48-h mobility 96 N/A Kuhn and Pattard (1990)

A Scenedesmus subspicatus 48-h growth 0.028 N/A Kuhn and Pattard (1990)

A Scenedesmus subspicatus 48-h growth 0.07 N/A Kuhn and Pattard (1990)

Other Chemicals

Sodium bisulfite F Carassius spp. 96-h survival 100 N/A MSDS Solvay Chemicals (2007)

F Gambusia affinis 96-h survival 240 N/A US EPA ECOTOX (Wallen et al. , 1957)

C Daphnia magna 96-h survival 102 N/A US EPA ECOTOX (Freeman and Fowler, 1953)

C Daphnia magna 50-h survival 81 N/A US EPA ECOTOX (Dowden and Bennett, 1965)

C Daphnia magna 24-h survival 171 N/A US EPA ECOTOX (Dowden and Bennett, 1965)

A Skeletonema

costatum 96-h growth 224 128 Nautilus Environmental,
2009

F = fish, C = crustacean, A = algae, Am = amphibian, Ci = ciliate, N/A = not applicable.

### MEPC 61/2/9 Annex, page 17

I:\MEPC\61\2-9.doc 

### Table 3 summarizes acute aquatic toxicity testing results for treated discharge samples, post-neutralization, from the BalPure ® 

### system. Toxicity tests were conducted with six taxonomic groups including bacteria, algae, crustaceans, rotifers, mollusks and fish in two water types: brackish water (low salinity) and marine water (high salinity). The samples were collected for toxicity testing on Day 1 and Day 5 after ballast water treatment and neutralization. Toxicity

was indicated in one acute test with Acartia tonsa one day after BalPure ® 

### treatment (NOEC of 18%). Discussion of the whole effluent toxicity data is located in section 11.4.

Table 3: Acute Aquatic Ecotoxicity Data - Land-based Testing

Substance F
C

A

MB

R Species Test Type Days
after

treatment E(L)C 50 % sample NOEC
% sample Reference/
Comments

Low Salinit y (23.68 PSU)

BalPure ®

Treatment

Dose: 14.83 mg/L (ave.) C Acartia tonsa 48h mobility (ISO 14669) 1 >100 18 Grontmij|AquaSense, 2009 5 >100 100 Grontmij|AquaSense, 2009

M Crassostrea gigas 48h larval development (ASTM E724) 1 >100 100 Grontmij|AquaSense, 2009

5 >100 100 Grontmij|AquaSense, 2009

B Vibrio fischeri 30m inhibition of light emission (ISO 11348-3) 1 >90* N/R Grontmij|AquaSense, 2009

5 >90* N/R Grontmij|AquaSense, 2009

A Phaeodactylum
tricornutum 72h growth

inhibition (ISO 10253) 1 >100 100 Grontmij|AquaSense, 2009

5 >100 100 Grontmij|AquaSense, 2009

R Brachionus plicatilis 24h survival (MircoBioTests Inc.) 1 >100 100 Grontmij|AquaSense, 2009 5 >100 100 Grontmij|AquaSense, 2009

F Scophthalmus

maximus 96h survival (OECD 203) 1 >100 100 Grontmij|AquaSense, 2009 5 >100 100 Grontmij|AquaSense, 2009 High Salinit y (33.90 PSU)

BalPure ®

Treatment

Dose: 13.17 mg/L (ave.) C Acartia tonsa 48h mobility (ISO 14669) 1 >100 100 Grontmij|AquaSense, 2009 5 >100 100 Grontmij|AquaSense, 2009

M Crassostrea gigas 48h larval development (ASTM E724) 1 >100 100 Grontmij|AquaSense, 2009

5 >100 N/D Grontmij|AquaSense, 2009

B Vibrio fischeri 30m inhibition of light emission (ISO 11348-3) 1 >90* N/R Grontmij|AquaSense, 2009

5 >90* N/R Grontmij|AquaSense, 2009

A Phaeodactylum
tricornutum 72h growth

inhibition (ISO 10253) 1 >100 100 Grontmij|AquaSense, 2009

5 >100 100 Grontmij|AquaSense, 2009

R Brachionus plicatilis 24h survival (MircoBioTests Inc.) 1 >100 100 Grontmij|AquaSense, 2009 5 >100 100 Grontmij|AquaSense, 2009

F Scophthalmus

maximus 96h survival (OECD 203) 1 >100 100 Grontmij|AquaSense, 2009 5 >100 100 Grontmij|AquaSense, 2009

F = fish, C = crustacean, A = algae, M = mollusk, B = bacteria, R = rotifer. N/D = not determined; N/R = not reported. *Maximum tested concentration = 90% vol. of sample.



### 3.2 Chronic aquatic ecotoxicity

Table 4 summarizes the data found in literature concerning chronic aquatic toxicity for the

substances associated with the BalPure ® 

### system. Literature concerning chronic aquatic toxicity for several HAAs could not be located to compile a complete data set (fish, crustaceans, algae). Similar data gaps are also noted in other dossiers submitted for approval under Procedure (G9), suggesting that other literature searches have had similar findings. However, if available, data using alternative endpoints (EC 03 

### ) is included as supporting information.

### MEPC 61/2/9 Annex, page 18

I:\MEPC\61\2-9.doc 

### Table 4: Overview of Chronic Aquatic Ecotoxicity Data

Substance F
C

A Species Test Type E(L)C 50 mg/L NOEC mg/L Reference/
Comments

Active Substance

TRO as Cl 2 (Fresh water) F Ictalurus punctatus 134-d growth N/A 0.005 Hermanutz et al. (1990)

C Gammarus pseudolimnaeus 70-d fecundity N/A 0.012 Arthur et al. (1975)

A Natural algae 24-d inhibition of

biomass N/A 0.079 Pratt et al. (1988)

TRO as Cl 2 (Saltwater) F Menidia peninsula 32-d egg to post-hat ch N/A 0.04 Goodman et al. (1983)

C Panaeus kerathurus 7-d growth/molting N/A 0.079 Saroglia and Scarano (1979)

A Natural phytoplankton 21-d reduction in cell density N/A 0.001 Sanders et al. (1981)

Hypochlorous

acid F Oncorhynchus

kisutch 23-d survival N/A 0.101 US EPA ECOTOX (Holland et al., 1960)

C Americamysis bahia 7-d reproduction N/A 0.048 Fisher et al. (1994) Hypobromous
acid No data found in literature

Relevant Chemicals

Bromate F Morone saxatilis 10-d survival 92.6 -- Richardson et al. (1981)

F Leiostomus
zanthurus 10-d survival 278.6 -- Richardson et al. (1981)

A Thalassiosira pseudonana 7-d growth inhibition 16 -- US EPA ECOTOX (Erickson and Freeman, 1978)

2,4,6- Tribromophenol F Pimephales promelas 8-d survival 4.5 N/A US EPA ECOTOX (Phipps et al., 1981)

C Daphnia magna 21-d reproduction rate N/A 0.10 OECD SIDS (2003)

A Selenastrum capricornutum 72-h biomass N/A 0.22 OECD SIDS (2003)

A Selenastrum capricornutum 24-72-h growth N/A 1.0 OECD SIDS (2003)

THMs

Chloroform F Oryzias latipes 9- month growth N/A 1.5 Toussaint et al. (2001)

C Daphnia magna 21-d reproduction N/A 13 US EPA ECOTOX (Kuhn et al., 1988)

A Skeletonema

costatum 5-d reduction in cell

volume 477 216 Cowgill et al. (1989)

Bromoform F Cyprinodon variegates 28d- growth N/A 8.5 US EPA ECOTOX (Ward et al., 1981)

A Pseudokirchneriella subcapitata 96-h biochemistry change N/A 38.6 U.S. EPA ECOTOX (1978)

Dichlorobromomethane No data found in literature

Chlorodibromomethane No data found in literature

HAAs

Dichloroacetic
acid A Scenedesmus subspicatus 7-d cell proliferation 1485 (EC03) N/A US EPA ECOTOX (Trenel and Kuhn, 1982)

Dibromochloroacetic acid No data found in literature

Dibromoacetic

acid No data found in literature

Tribromoacetic

acid No data found in literature

Trichloroacetic

acid A Scenedesmus quadricauda 7-d growth threshold N/A 200 OECD SIDS (2000)

A Chlorella vulgaris 4d-population change N/A 100 US EPA ECOTOX (Garten, 1990)

Bromochloroacetic acid No data found in literature

### MEPC 61/2/9 Annex, page 19

I:\MEPC\61\2-9.doc

Substance F
C

A Species Test Type E(L)C 50 mg/L NOEC mg/L Reference/
Comments

Monobromoacetic acid C Daphnia magna 21d-NOEC N/A 3.2 US EPA ECOTOX (Kuhn, 1988)

C Daphnia magna 21d-NOEC on reproduction N/A 1.6 US EPA ECOTOX (Kuehn et al , 1989)

A Scenedesmus subspicatus 3d-population change N/A 1.4 Kuhn and Pattard (1990)

Monochloroacetic acid C Daphnia magna 21d-reproduction change N/A 32 Kuhn and Pattard (1990)

A Scenedesmus subspicatus 7d-histology 0.13 (EC03) N/A US EPA ECOTOX (Trenel and Kuhn, 1982)
Other Chemicals

Sodium
bisulfite No data found in literature

F = fish, C = crustacean, A = algae, N/A = not applicable.



### Results for chronic whole effluent toxicity (WET) testing of treated/neutralized ballast water discharge are summarized in Table 5 below and discussed further in section 11 "Evaluation of treated ballast water". Samples were drawn from the land-based test set-up and no chronic toxicity was observed for any specie s tested. The highest concentration with no observed effect (NOEC) was 100 per cent sa mple (Grontmij|AquaSense, 2009). As agreed upon with the German Administration, chronic testing was performed only for organisms that had effects noted during acute testing. As acute effects were only observed during one of
four acute tests with Acartia tonsa (NOEC 18%), STDN also performed chronic (sub-lethal) testing for fish. The data indicate that no chronic effects were noted for either species tested.

Table 5: Chronic Aquatic Ecotoxicity Data – Land-based Testing

Substance F
C Species Test Type Days
after

treatment E(L)C 50 % sample NOEC
% sample Reference/
Comments

Low Salinity (23.68 PSU)

BalPure ®

Treatment

Dose: 14.83 mg/L (ave.) C Acartia tonsa 30d repro./devel. (ASTM STP 667) 1 N/D 100 Grontmij|AquaSense, 2009 5 N/D 100 Grontmij|AquaSense, 2009

F Scophthalmus

maximus 48h develop (PARCOM 1994) 1 >100 100 Grontmij|AquaSense, 2009

5 >100 100 Grontmij|AquaSense, 2009

High Salinity (33.90 PSU)

BalPure ®

Treatment

Dose: 13.17 mg/L (ave.) C Acartia tonsa 30d repro./devel. (ASTM STP 667) 1 N/D 100 Grontmij|AquaSense, 2009 5 N/D 100 Grontmij|AquaSense, 2009

F Scophthalmus

maximus 48h develop (PARCOM 1994) 1 >100 N/D Grontmij|AquaSense, 2009

5 >100 100 Grontmij|AquaSense, 2009

F = fish, C = crustacean, N/D = not determined.



### 3.3 Endocrine disruption

Endocrine disrupting chemicals (EDCs) are defined as exogenous substances that cause adverse effects in an organism or its progeny, consequent to changes in endocrine functions. In a recently conducted study to investigate whether chlorinated by-products formed through waste water disinfection were estrogenic, no relationship was found between the formation of THMs and estrogenic activity (Schiliro, 2009). In fact, chlorination of surface water and effluents was found to decrease estrogenic activity, which is thought to be due to the oxidation effects of chlorine (Lee, 2004). A thorough review of the literature found no indications that
either of the Active Substances in the TRO as Cl 2 

### (HOCl/HOBr) or th e chemically more complex THMs/HAAs were EDCs.

### MEPC 61/2/9 Annex, page 20

I:\MEPC\61\2-9.doc 

### Brominated phenols have been shown to cause a significant effect on the Ca 2+ 

### homeostasis in endocrine cells by causing an intracellular increase in Ca 2+ 

### (Hassenklöver et al ., 2006). At concentrations of 300 μM or higher this effect may suggest a link to endocrine disruption by 2,4,6-tribromophenol (TBP). Due to the low concentration of 2,4,6-TBP (maximum concentration of 1.3 μg/L) (Tables 22 and 23) detected in treated ballast water, and the limited routes of exposure in environmental waters, no endocrine effects would be expected as a result of treated ballast water discharge.

3.4 Sediment toxicity

The sediment toxicity of a chemical is a function of the ability of the chemical to be adsorbed to sediment as well as its persistence and toxicity. The organic carbon partition coefficient (Koc) is a measure of the tendency of an organic substance to be adsorbed by soil or sediment. STDN's application dossier for Basic Approval (MEPC 60/2/9, section 3.4) provided data for THMs/HAAs measured in previous studies of the BalPure ® 

### system. During land-based testing, additional DBPs were analysed and three were found in measurable concentrations. Data for these three additional substances is provided below.

The Koc for 2,4,6-TBP (1,186 L/kg) indicates moderate partitioning into sediment. When 2,4,6-TBP is released to water, 93% is expected to stay in the water compartment and 7% is transported to the sediment compartment (OECD SIDS, 2003). 2,4,6-Tribromophenol is reported to dehalogenate rapidly in anaerobic sediments, with a reported half-life of approximately 4 days (CICADS 66, 2005). This is much more rapid than the sediment persistence criteria of 180 days in marine s ediment and 120 days in fresh water sediment (Table 19 and the Methodology for information gathering and the conduct work of the GESAMP-BWWG (Methodology), section 6.1.4). Considering the low concentration of 2,4,6-TBP (maximum = 1.3 μg/L) in ballast water discharge, a moderate potential for sediment adsorption, and the rapid sediment degradation, no effects on sediment are expected as a result of the BalPure ® 

### system.

Based on the low Koc values for dibromochloroac etic acid (DBCAA) and tribromoacetic acid (TBAA) (3.23 L/kg and 5.3 L/kg, respectively), these substances are not expected to partition into sediment. Therefore, no sediment toxicity impacts are anticipated as a result of

BalPure ® 

### ballast water discharge.

Table 6: Koc Values for Relevant Chemicals

Substance Koc (L/kg) Reference/Comments

Relevant Chemicals 2,4,6-Tribromophenol (TBP) 1,186 OECD SIDS (2003)

HAAs Dibromochloroacetic acid (DBCAA) 3.23 EPI Suite v4.0 Tribromoacetic acid (TBAA) 5.3 HSDB/TOXNET (2009)



### 3.5 Bioavailability/biomagnification/bioconcentration

The bioconcentration factor (BCF) is the concentration of a particular chemical in a tissue per concentration of chemical in water (reported as L/kg). This physical property characterizes the accumulation of pollutants through chemical partitioning from the aqueous phase into an organic phase, such as fish or other aquatic organism tissues. The BCF is the best measure of bioavailability, biomagnification, and bioconcentration. Typical BCFs for organic chemicals in fish and most aquatic invertebrates are in the 500-1,000 L/kg range. STDN's application dossier for Basic Approval (MEPC 60/2/9, section 3.5) provided data for THMs/HAAs measured in previous studies of the BalPure ® 

### system. During land-based testing, additional DBPs were analysed and three were found in measurable concentrations. Data for these three additional substances is provided below.

### MEPC 61/2/9 Annex, page 21

I:\MEPC\61\2-9.doc 

### The BCFs summarized in Table 7 below are all well below 2,000 L/kg (Methodology, section 6.1.4 and Table 19 of this document), indicating that they are unlikely to bioconcentrate/bioaccumulate in aquatic organisms or present a food chain risk.

Table 7: BCFs for Relevant Chemicals

Substance BCF (L/kg) Reference / Comments

Relevant Chemicals 2,4,6-Tribromophenol (TBP) 83 - 513 HSDB/TOXNET (2009)

HAAs Dibromochloroacetic acid (DBCAA) 3.16 EPI Suite v4.0 Tribromoacetic acid (TBAA) 0.63 HSDB/TOXNET (2009)



### 3.6 Food web/population effects

Population and food web effects can occur if substances have properties that tend to bioaccumulate and/or persist in the environm ent. Little biomagnification and persistence in aquatic and mammalian food webs is anticipated from the Relevant Chemicals. This conclusion is based on the low Koc values for DBCAA and TBAA. Additionally, the BCFs for DBCAA and TBAA are well below 500 L/kg indicating that bioconcentration/bioaccumulation is not expected to occur in aquatic organisms. Although the Koc for 2,4,6-TBP indicates a moderate potential to be transported to the sediment compartment, and a BCF range of 83-513 L/kg indicates moderate bioconcentration/ bioaccumulation potential, the concentration of 2,4,6-TBP measured in treated/neutralized ballast water was very low (maximum = 1.3 μg/L). In one case, 2,4,6-TBP had higher measurable concentration in the control than in the treated/neutralized ballast water sample (Table 23). Therefore, no food web and/or population effects can be expected as a result of
these Relevant Chemicals in BalPure ® 

### ballast water discharge.

4 DATA ON MAMMALIAN TOXICITY (G9: 4.2.1.2)

STDN's application dossier for Basic Approval (MEPC 60/2/9, section 3.4) provided data for DBPs measured during previous studies of the BalPure ® 

### system. During land-based testing at NIOZ, additional DBPs were analysed for and three substances were found in measurable concentrations. Mammalian toxicity data for these three additional substances is provided in Tables 8 to 16 below. Information on all prev iously measured substances was presented in the Basic Approval dossier (MEPC 60/2/9).

In the mammalian toxicity studies reviewed, the chemicals were tested for various exposure routes (oral, dermal, etc.) and/or chemical forms, which do not necessarily reflect the actual potential exposure routes or chemical forms associated with the BalPure ® 

### system. In some cases, data could not be located in available literature.

4.1 Acute mammalian toxicity

Table 8: Acute Mammalian Toxicity Data

Substance Exposure Route Species V alue Range Reference/
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) a. Acute Oral LD 50 b. Inhalation LC 50 c. Acute Dermal LD 50 a. Rat
b. Rat

c. Rabbit a. >5000 mg/kg b. >50 mg/L/4hr c. >8000 mg/kg a. CICADS 66 (2005) b. CICADS 66 (2005) c. CICADS 66 (2005)

HAAs

Dibromochloroacetic acid (DBCAA) Limited toxicology data available. -- -- Richardson et al. (2007)

Tribromoacetic acid (TBAA) Limited to xicology data available. -- -- Richardson et al. (2007)

### MEPC 61/2/9 Annex, page 22

I:\MEPC\61\2-9.doc 

### 4.2 Effects on skin and eye

Table 9: Effects on Skin and Eye

Substance Skin Ey e Sensitization Reference /
Comments

Relevant Chemicals 2,4,6-Tribromophenol (TBP) Not irritating to rabbits Moderately irritating to rabbits Skin sensitizer in guinea-pigs CICADS 66 (2005)

HAAs

Dibromochloroacetic acid (DBCAA) May be harmful if absorbed through skin;

causes skin burns Causes eye burns No data found in

literature Sigma Aldrich MSDS (2009)

Tribromoacetic acid (TBAA) a) Corrosive; causes burning sensation, and is
destructive to tissue of
mucous membranes of

skin a) Destructive to
tissue of the

mucous membranes of

eyes b) No sensitizing
effect known. a) HSDB/TOXNET (2009) b) Alfa Aesar MSDS

(2009)



### 4.3 Repeated-dose toxicity

Table 10: Repeated-dose Toxicity

Substance Exposure Route Species Value Range Reference/
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) Oral, 48 day subchronic reproduction/developmental Rat NOAEL 100 mg/kg body weight/day CICADS 66 (2005)

HAAs

Dibromochloroacetic acid (DBCAA) Limited toxicology data

available. -- -- Richardson et al. (2007)

Tribromoacetic acid (TBAA) Limited toxicology data
available. -- -- Richardson et al. (2007)



### 4.4 Chronic mammalian toxicity

Table 11: Chronic Mammalian Toxicity

Substance Exposure Route Species Value Range Reference/
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) No long term exposure

studies on brominated phenols were identified. -- -- CICADS 66 (2005)

HAAs

Dibromochloroacetic acid (DBCAA) -- -- -- No data found in

literature

Tribromoacetic acid (TBAA) -- -- -- No data found in

literature

### MEPC 61/2/9 Annex, page 23

I:\MEPC\61\2-9.doc 

### 4.5 Developmental and reproductive toxicity

Table 12: Summary of Developmental and Reproductive Toxicity Data

Substance Exposure Route Species Effects Reference/
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) Oral gavage, doses
from 10- 3000 mg/kg/day, on gestation days 6-15 Rats No effect on fertility, growth, or survival at doses of 200 mg/kg/d or less; Slight decrease in body weight and decrease
in number of viable fetuses in 1000 mg/kg/d; NOAEL 300 mg/kg/d CICADS 66 (2005)

HAAs

Dibromochloroacetic acid (DBCAA) 26- hour Embryo

exposure; Concentrations 1500-2500 μM DBCAA Mice ≥ 1500 μM increased the number of dysmorphic embryos with prosensephalic hypoplasia and eye defects were observed;

≥ 2000 μM caused heart dysmorphology and abnormal yolk sac morphology;

≥ 2500 μM caused failure to develop Hunter et al. (2006)

Tribromoacetic acid (TBAA) a) Oral, tribromoacetic acid in drinking water, 14 days, doses up to 400 ppm TBAA b) 24-26 hours Embryo

exposure; Concentrations from 0-5,000 μM TBAA Rats a) No effects on reproductive function, as a general toxicant, or as reproductive
toxicant in males

b) ≥ 3,000 μM TBAA induced malformation effects; nonclosure of the

cranial neural tube and reduction in development of bulbus cordis a) NTP (1998)

b) Hunter

et al. (1996)



### 4.6 Carcinogenicity

Table 13: Summary of Data on Carcinogenicity

Substance Carci nogen Classification Description Reference/
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) a. Not classified by NTP b. Not classified by IARC c. No carcinogenicity studies

on brominated phenols
were identified. -- a. NTP (2009) b. IARC (2009) c. CICADS 66 (2005)

HAAs

Dibromochloroacetic acid (DBCAA) a. Not classified by NTP b. Not classified by IARC Oral exposure in drinking water; 2 years; shown to induce tumours in the livers of mice; limited details on test doses; references c. and d.
identified DBCAA has cancer potential and is currently under study a. NTP (2009) b. IARC (2009)

c. Richardson et al.

(2007)

d. Woo et al. (2002)

Tribromoacetic acid (TBAA) a. Not classified by NTP b. Not classified by IARC c. Likely to be we akly carcinogenic; or carcinogenic toward a single species/target at relatively high doses based on structure-activity relationship (SAR) analysis a. NTP (2009) b. IARC (2009)

c. Woo et al. (2002)

### MEPC 61/2/9 Annex, page 24

I:\MEPC\61\2-9.doc 

### 4.7 Mutagenicity and genotoxicity

Table 14: Summary of Data on Mutagenicity and Genotoxicity

Substance Study Results Reference /
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) Tested in Salmonella /microsome preincubation assay with doses 0-333 μg/plate in Salmonella typhimurium strains TA98, TA100, TA1535, and TA1537 in presence and absence of
Aroclor-induced rat/hamster live r S9; highest nonmutagenic test dose = 100 μg/plate causing a slight clearing in background lawn

above this dose level HSDB/TOXNET (2009)

HAAs

Dibromochloroacetic acid (DBCAA) Limited mutagenicity / genotoxicity studies on DBCAA available. Richardson et al. (2007)

Tribromoacetic acid (TBAA) Studies show TBAA causes mutagenic and genotoxic responses

in Salmonella typhimurium strain TA100 in a) fluctuation and microsuspension assays and b) in SOS chromotest a. Nelson et al. (2001)
b. Giller et al. (1997)



### 4.8 Toxicokinetics

Table 15: Summary of Uptake, Absorption, and Excretion of Chemicals

Substance Study Results Reference/
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) After administration of a single oral dose (4.04-5.34 mg/kg) to rats the substance was rapidly absorbed from gastro-intestinal tract; 77% excreted via urine, 2-14% eliminated in feces within 48 h;

blood t 1/2 was 2.03 h OECD SIDS (2003)

HAAs

Dibromochloroacetic acid (DBCAA) After administration of a single dose (25 μmol/kg) by iv rats, plasma elimination of DBCAA was rapid with t 1/2 of 1.6 h; dose urinary recovery was 33%; Same dose given by gavage yielded plasma elimination t 1/2 of 4.59 h; 40-70% of total body clearance

due to metabolic clearance Saghir & Schultz (2005)

Tribromoacetic acid (TBAA) After administration of a single dose (25 μmol/kg) by to rats,
elimination of TBAA was rapid with t 1/2 of 46 min; dose urinary recovery was 8%; Same dose given by gavage yielded plasma

elimination t 1/2 of 2.11h; 40-70% of total body clearance due to

metabolic clearance Saghir & Schultz (2005)



### 5 DATA ON ENVIRONMENTAL FATE AND EFFECT UNDER AEROBIC AND ANAEROBIC CONDITIONS (G9: 4.2.1.3)

5.1 Modes of degradation (biotic; abiotic)

STDN's application dossier for Basic Approval (MEPC 60/2/9, section 3.4) provided degradation data for DBPs measured during previous studies of the BalPure ® 

### system. During land-based testing at NIOZ, additional DBPs were analysed and three substances were found in measurable concentrations. Degradation data for these three additional substances is provided in Table 16 below.

### MEPC 61/2/9 Annex, page 25

I:\MEPC\61\2-9.doc 

### Table 16: Fate and Mode of Degradation for Relevant Chemicals

Substance Fate/Effect Under
Aerobic/Anaerobic
Conditions Modes of Degradation Reference/
Comments

Relevant Chemicals

2,4,6-Tribromophenol (TBP) Anaerobic: reported to dehalogenate rapidly in anaerobic sediments, half-life of approx. 4 days (CICADS 66, 2005) Biotic: BOD 49% after 28 days in activated sludge; 82% degraded in 3-day biodegradation test in river water. Abiotic: Stable in water and not hydrolyzed regardless of pH; Direct photolysis by UV
in air indicates a half life of 4.6 hours CICADS 66 (2005)

HAAs

Dibromochloroacetic acid (DBCAA) No data located. Biotic and Abiotic: demonstrated in study

with and without microbial inhibitors in which degradation occurred in both experiments. Hashimoto et al. (1998)

Tribromoacetic acid (TBAA) Aerobic: Used as carbon source by Pseudomonas

and Nocardia when
measured for halide release over 20 days (30oC) Biotic: microbial degradation demonstrated (Hashimoto et al., 1998) Abiotic: Atmospheric half-life = 30.9 days; not expected to undergo hydrolysis or susceptible to direct photolysis by UV HSDB/TOXNET (2009)



### 5.2 Bioaccumulation, partition coefficient, octanol/water partition coefficient

Based on the data presented for degradation in Table 16 above, the BCFs presented in Table 7, and Koc values in Table 6, these additional substances associated with the STDN BalPure ®


### system have a low likelihood of bioaccumul ation and partitioning to aquatic sediments.

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

Higher tier simulation tests are not required; this section is not applicable.

5.4 Reaction with organic matter

The formation of disinfection by-products (DBPs) when using chlorine-based water disinfection methods is well known. DBP formation is a result of disinfectant reactions with natural organic matter, often measured as total organic carbon (TOC), which serves as the organic precursor (IPCS, 2000). Two major classes of DBPs that are commonly formed in chlorine treated water include THMs and HAAs (Westerhoff, et al., 2003). Both of these DBP classes have been

measured in water treated with the BalPure ® 

### system. Water quality (e.g., pH, temperature, bromide level, TOC) and treatment conditions (e.g., hypochlorite dose, contact time, removal of organic matter prior to treatment) influences the formation of DBPs as a result of organic matter reactions. Further, the distribution of DBP species (up to four THM species, up to nine HAA species) is affected by the amounts of TOC, bromide and chlorine present (IPCS, 2000).

Analysis to quantify DBP concentrations in ballast water discharge was conducted during land-based testing of the BalPure ® 

### system at NIOZ in 2009. Different water types (brackish, seawater) were treated/neutralized and then evaluated for DBPs. The data are presented in section 11, Tables 22 and 23.

5.5 Potential physical effects on wildlife and benthic habitats

When evaluated using GESAMP Reports and Studies No. 64, the chemical and physical properties of the Active Substances and Relevant Chemicals associated with the BalPure ®


### system as presented in STDN's application do ssier for Basic Approval (MEPC 60/2/9, Tables 17 to 21) and in Table 17 below indicate that physical effects on wildlife and benthic habitats as described are not expected to occur.

### MEPC 61/2/9 Annex, page 26

I:\MEPC\61\2-9.doc 

### 5.6 Potential residues in seafood

Chemicals measured in treated ballast water discharge may pose a threat to seafood consumers only if they tend to bioaccumulate (within a trophic level, an increase in concentration of a substance in tissues due to uptake from food and sediments) or biomagnify (an increase in the concentration of a substance in the food web). The bioaccumulation criteria per the Methodology (MEPC 58/2/7, annex 4) include an octanol-water partition coefficient (Log K
ow 

### ) of ≥ 3 or a bioconcentration factor (BCF) >2000. With the exception of 2,4,6-tribromophenol, the chemicals presented in STDN's application dossier for Basic Approval (MEPC 60/2/9) and identified in this risk assessment all have Log Kow values less than 3. However, based on the discussion for 2,4,6-TBP in section 3.4 above, and the fact that the BCFs for all substances are less than 2000, the substances are not expected to bioaccumulate, persist in the food web, or cause tainting of seafood.

6 PHYSICAL AND CHEMICAL PROPERTIES FOR THE ACTIVE SUBSTANCES, RELEVANT CHEMICALS, AND TREATED BALLAST WATER (G9: 4.2.1.4)

STDN's application dossier for Basic Approval (M EPC 60/2/9, section 3.4) provided chemical and physical property data for Active Substanc es and relevant DBPs measured in treated ballast water during previous studies of the BalPure ® 

### system. The Basic Approval dossier also presented the chemical and physical properties of treated ballast water. During land-based testing at NIOZ, additional DBPs were analysed and three substances were
found in measurable concentrations. Availabl e chemical property data for these three additional substances is provided in Table 17 below.

Table 17: Physical and Chemical Properties of Relevant Chemicals

Physical/Chemical Properties 2,4,6-Tribromophenol Dibromochloroacetic

acid Tribromoacetic acid

Melting Point (oC) 93.9 (CICADS 66, 2005) 151.68 (EPI Suite, 2009) 129-135 (HSDB/TOXNET, 2009) Boiling point (oC) 244 (CICADS 66, 2005) 263.59 (EPI Suite, 2009) 245 (HSDB/TOXNET, 2009) Flammability (flash point for liquids; oC) Not available Not available Not available

Density (20oC; kg/m 3 ) 2550 (Alfa Aesar MSDS, 2009) Not available Not available

Vapour pressure/Vapour density (air=1) 4.2 x 10 - 2 Pa (CICADS 66, 2005) 0.692 Pa (EPI Suite, 2009) 3.73 x 10 - 2 Pa (HSDB/TOXNET, 2009) Water solubility (temp; effect of pH; mg/L)/

Dissociation constant (pKa) 59 mg/L (25oC) / pka = 6.08 (CICADS 66, 2005) 2353 mg/L (25oC) (EPI Suite, 2009) 2.0 x 10 5 (25oC) / pka = 0.72 (HSDB/TOXNET, 2009)

Oxidation/Reduction potential ORP of natural seawater ORP of natural seawater ORP of natural seawater

Corrosivity to materials Not avai lable Not available Not available Auto-ignition temperature (oC) Not available Not available Not available

Explosive properties Not explosive (Alfa Aesar MSDS, 2009) Not available Not explosive (Alfa Aesar MSDS, 2009) Oxidizing properties No available Not available Not available

Surface tension Not available Not available Not available Viscosity (20oC) Not available Not available Not available Thermal stability Stable Stable Stable Reactivity to container
material Not stored; produced in situ Not stored;
Produced in situ Not stored; produced in situ

Other knowns None None None

### MEPC 61/2/9 Annex, page 27

I:\MEPC\61\2-9.doc 

### 7 ANALYTICAL METHODS AT ENVIRONMENTALLY RELEVANT CONCENTRATIONS (G9: 4.2.1.5)

7.1 Analysis of Total Residual Oxidants (TRO as Cl 2 

### )

TRO (as Cl 2 

### ) is measured at two concentration ranges (high and low) using two different analytical procedures. An iodometric titration procedure is used to measure higher range TRO (as Cl 2 

### ) in the product stream exiting the BalPure ® 

### unit. Concentrations are typically 1,000 mg/L and this procedure is accepted by the American Water Works Association (AWWA) for examination of water and waste water. The procedure is only used if needed to perform diagnostics on the BalPure ® 

### system, and is included in appendix A.5. A second method is typically used for measuring lower range TRO (as Cl 2 

### ) in potable water and waste water streams. A Hach colourimeter can be used to measure the TRO (as Cl 2 

### ) in ballast tanks and in the deballast stream pre- and post-neutralization. The TRO (as Cl 2 

### ) oxidizes triiodide ion (I 3 - 

### ) to iodine (I 2 

### ). The iodine and free chlorine react with DPD (N,N-diethyl- p -phenylenediamine) to form a red solution. The colour intensity is proportional to the TRO concentration. This method is also provided in appendix A.5.

During land-based testing at NIOZ, TRO (as Cl 2 

### ) measurements were performed with a Hach Pocket Colorimeter using Hach Method 8167 (e quivalent to EPA Method 330.5). For TRO (as Cl 2 

### ) in the 0.1 mg/L to 8.0 mg/L range the method has a detection limit of 0.1 mg/L. For TRO (as Cl 2 

### ) in the 0.02 mg/L to 2 mg/L range the method has a detection limit of 0.02 mg/L. Residual sodium bisulfite in post-neutralization discharge samples was measured using the
Hach SU-5 test kit with a titration/iodometric method. Information on the above methods is provided in Table 18 and appendix A.5.

7.2 Analysis of Disinfection By-products (DBPs)

Treated ballast water samples were collected immediately after neutralization at discharge. Samples for chemical analysis were stored in proper sample containers at 4°C and transported to the designated laboratory within 24 hours of collection. Analysis of the samples occurred within the time specified under standard laboratory procedures. Qualified and accredited laboratories were utilized for analysis of treated water samples. Acceptable field-testing analytical methods were also used where applicable (e.g., TRO (as Cl 2 

### ) and bisulfite). The methods used to determine DBP concentrations are listed in Table 18 below and more details are provided in appendix A.5. Information regarding quality assurance from the analytical laboratories is included in appendix A.6.

Table 18: Analytical Methods

Substance/Paramete r Method Description Detection Limit TRO (as Cl 2 ) High Range: 0.1-8.0 mg/L Low range: 0.02-2.0 mg/L Hach Method 8167 (Equivalent to US EPA Method 30.5) DPD, Colorimetric High Range: 0.1 mg/L 1
Low Range: 0.02 mg/L 1

Bisulfate measured as sulfate ion NEN-EN -ISO 10304-1 Ion chromatography 1.0 mg/L 1

Bisulfite measured as sulfite ion Hach Te st Kit SU-5 Titration/Iodometric 1 mg/L 1
THMs NEN-EN-ISO 15680 Gas chromatography 0.1 μ g/L HAAs US EPA Method 552.2 Gas chromatography 1.0 -10 μ g/L 3
2,4,6-Tribromophenol US EPA Method 528 Gas chromatography 0.1-0.2 μ g/L 3
Monobromoacetonitrile US EPA Method 524.1 Gas chromatography 1-10 μ g/L 3

Bromate US EPA Method 317 Ion chromatography 10 μg/L 2
Chlorate US EPA Method 300.1 Ion chromatography 50 μg/L 2

1 = Method Detection Limit (MDL).

2 = Minimum Reporting Level (MRL).

3 = Limit of Detection (LOD).

### MEPC 61/2/9 Annex, page 28

I:\MEPC\61\2-9.doc 

### 8 USE OF ACTIVE SUBSTANCE

8.1 Manner of application

The BalPure ® 

### system can service ships with ballast water flow requirements from 100 to 10,000 cubic metres per hour. The BalPure ® 

### system size (electrolytic cell size) is defined by the ship's designed ballast water flow rate, but because the system has a 100% turn down capability the hypochlorite production rate is matched to the actual measured ballast flow rate. Treatment is done during ballasting operations allowing the biocide solution to be generated anywhere on the ship and injected as needed. This would apply to ships with one or multiple ballast systems or ships with multiple ballast pumps mounted within separate ballast tanks. The system can be del ivered as a complete system on one skid or divided into seven separate smaller skids based on specific unit operation (pumping, hypochlorite generation, hydrogen-hypochlorite separation, bisulfite storage, bisulfite metered addition, instrument and controls, and power rectification). This allows multiple skid locations as space is available throughout the vessel. The multiple skid design is perfect for retrofit applications and the one skid system is best for new buildings.

Operational control of the BalPure ® 

### system is accomplished by the main control panel attached to the hypochlorite generation unit or by a remote control panel that can be placed where most appropriate for a specific vessel. Together, the control panel and the transformer/rectifier unit comprise the main Programmable Logic Controller (PLC) control and rectification components. The control panel provides a visual display of the status of the rectifier DC voltage, current, and can alert the operator of any system alarms via the operator interface terminal (OIT). The main control panel also has a local emergency stop push button. All major equipment such as booster pumps, bisulfite metering pumps, and hydrogen
blowers can be controlled from the main cont rol panel. All monitoring equipment such as flow meters and ORP probes send the output in the form of 4-20 mA signals. All system control screens are password protected to limit oper ator modification to existing control logic. Only properly trained ship's crew members and BalPure ® 

### technicians will be allowed to access password-protected portions of the PLC.

Other system monitoring and control devices include a magnetic flow transmitter to monitor the flow of seawater at the electrolyzer inle t, transformer temperature switches that monitor the internal temperature of the rectifier, and airflow switches that monitor the hydrogen gas

dilution blowers.

8.1.1 Process flow description

The BalPure ® 

### system is designed to operate automatic ally and has two operation processes: ballasting and deballasting. During ballasting, the biocide solution is produced and injected into the ballast water intake piping (maximum treatment dose of 15 mg/L TRO as Cl 2 

### ); during deballasting sodium bisulfite is added directly to the ballast water discharge piping. The ballasting process is discussed first, followed by the deballasting process. A complete process flow diagram (PFD) of the system is included in appendix A.3. Figures 1 and 2 presented below provide a simplified overview of each phase of the treatment process.

8.1.1.1 Ballasting process – ballast water intake

Very generally, during the automatic ballasting process the system will sense that adequate seawater flow is available using a flow meter in the main ballast line. Once the system is primed with sufficient water (an approximate 1-minute cycle), the transformer/rectifier will supply DC current to the electrolyzer and initiate the electro-chemical generation process.

### MEPC 61/2/9 Annex, page 29

I:\MEPC\61\2-9.doc 

### The hypochlorite production rate is primarily tied to the ballast flow rate and achieves the pre-set required oxidant concentration by modulating the rectifier output amperage to coincide with the ballast flow rate. This is considered the large or gross adjustment. The produced oxidants are then injected into the main ballast line. If necessary, the system may also be operated manually. Figure 1 below prov ides an overview of the BalPure ® 

### ballasting process.

Figure 1: Overview of the BalPure ® Ballasting Process



### The BalPure ® 

### system remains in a stand-by mode until the flow meter in the main ballast line
detects ballast water flow and activates the BalPure ® 

### system. In the ballasting process,
seawater from the sea chest will be filtered with a 40 micron stainless steel mesh filtration unit. Filtration is only required during ballast uptake. If an installation requires that seawater be taken from a source other than filtered ballast water (e.g., seawater cooling) a duplex strainer filters the seawater to remove any particles larger than 800 microns. Using an inline booster pump, the BalPure ® 

### system typically receives <1% of the total incoming ballast water flow as a side- stream off the main ballast intake line. The booster pump increases the line pressure to provide proper flow through the hypochlorite generation unit and allow solution injection into the main ballast line. An inlet flow transmitter, designed to protect the treatment system, will automatically shut down the electrical current to the electrolyzer should seawater flow through the electrolyzer drop below 80% of the design flow rate. The filtered seawater passes through a heat sink where it absorbs excess heat generated by the silicon-controlled rectifiers. The seawater then passes through a series of electrolytic cells which are connected to the transformer/rectifier. The electrolyzer units then generate the Active Substance along with hydrogen gas as a by-product.

Immediately after exit from the electrolytic cells, the combined seawater/biocide solution (liquid) and hydrogen (gas) is delivered to a patented cyclone separation device where the hydrogen is separated from the biocide/seawater solution. Hydrogen gas does not enter the ballast water piping or tanks. The hydrogen gas is directed to a vent stack where it is diluted by forced air blowers and vented to the atmo sphere outside of the ship. To ensure proper ventilation the vent line is serviced by two redundant blowers coupled to sail switches.

### MEPC 61/2/9 Annex, page 30

I:\MEPC\61\2-9.doc 

### The sail switches ensure proper air flow to dilute the air stream to <1% hydrogen. The LEL for hydrogen is 4% and the operating limitations on the system provide a four-fold safety factor. The PLC monitors proper air flow and will shut down the system, resulting in an alarm condition if proper ventilation air flow is not maintained. Both blower motors and sail switches are tied to an automatic emergency shutdown for the production unit in the unlikely event all four devices fail. For additional safety, a hydrogen sensor with alarm will be provided in the immediate proximity of the hypochlorite generation unit.

For optimum hypochlorite generator performance (i.e. to produce 90% of theoretical values), the inlet seawater temperature should be at least 15°C and have a sodium chloride concentration of at least 19,000 mg/L (19 PSU). However, the BalPure ® 

### system can operate at temperatures as low as 5°C and salinities of 10,000 mg/L (10 PSU). Less optimal conditions result in a slightly decreased hypochlorite production rate to 20% less than optimum. The hypochlorite production rate of the electrolytic cells is directly related to chloride ion availability and mobility. The salinity (PSU) of the source water determines the chloride ion availability, while temperature affects chloride ion mobility. These parameters impact the operating voltage of the electrolytic cells. For instance, when chloride ions are abundantly available and mobile, the operating voltage and hypochlorite production within the electrolytic cells will be optimum. If chloride ions and/or temperature are low, the operating voltage increases proportionally and hypochlorite production will be reduced. The BalPure ® 

### system is designed to adjust the hypochlorite production rate by monitoring the operating voltage of the electrolytic cells and increasing the rectifier operating amperage to sustain the TRO (as Cl 2 

### ) concentration required to treat incoming ballast water (maximum treatment dose of 15 mg/L TRO (as Cl 2 

### )). These adjustments are small and used to control the hypochlorite production rate to a narrow range (fine tuning).

The BalPure ® 

### system can also operate at higher salinities, such as ≥ 30,000 mg/L ( ≥ 30 PSU). In this case where chloride ions are highly abundant, the generator will only produce the design hypochlorite concentration. This is because higher salinity does not increase the efficiency or the production rate of the electrolytic cell beyond the optimum.

As mentioned above, the BalPure ® 

### unit is designed to operate in seawater with salinities

≥ 10 PSU. However, with minor process adjustments, the BalPure ® 

### unit can operate in fresh water. For operation in fresh water, an alternative supply of saltwater input to the

BalPure ® 

### unit is required. Because the BalPure ® 

### unit requires only a small amount (<1% of total incoming ballast flow), existing onboard alternative sources of seawater can be used.

By monitoring the operating voltage of the electrolytic cells and adjusting the amperage applied, the PLC programming of the BalPure ® 

### system guarantees effective operation over a wide temperature and/or PSU range.

8.1.1.2 Deballasting and neutralization process – ballast water discharge

In the deballasting process, the final phase of treatment, residual chlorine present in the ballast tank is neutralized (de-chlorinated) with sodium bisulfite just prior to discharge from the ship. The holding time that treated ballast water needs to be retained before discharge is discussed further in section 11.5. Neutralization is accomplished using ORP technology and bisulfite metering pumps. Two ORP probes are used; one confirms the presence of residual oxidant exiting the ballast tanks, while the second probe monitors and controls the addition of sodium bisulfite to neutralize TRO (as Cl 2 

### ) during ballast water discharge. The first ORP probe is located upstream of the bisulfite injection point, and the second ORP probe is located downstream of the bisulfite injection point.

During deballasting, the main ballast line filter used during the ballast uptake process is not required and is by-passed automatically.

### MEPC 61/2/9 Annex, page 31

I:\MEPC\61\2-9.doc Figure 2: Overview of the BalPure ® Deballasting Process



### ORP technology is based on the potential measur ement between two dissimilar metals within the ORP probe. ORP is not a quantitative measure of oxidant or bisulfite concentration but rather a qualitative measure that confirms the presence of oxidizing or reducing agents in the water. ORP technology allows for an in-line rapid determination of the amount of oxidation (or reduction) potential of the water. ORP is measured in millivolts (mV) and increases or decreases in direct relation with the oxidant residual in the water (Kelley, 2004). For example, natural waters have an ORP reading in the range of 100-150 mV. When hypochlorite is added to water, the ORP reading increases with an incr ease in hypochlorite dosage. Similarly, when a de-chlorinating agent such as sodium bisulfite is added to the water, the ORP reading will drop to a low mV level (Kelley, 2004). In this way, ORP measurements provide a practical and efficient method of optimizing water disinfection and controlling neutralizing agent dosage.

The BalPure ® 

### BWMS uses ORP readings as a general indicator of the presence/absence of residual oxidants, but STDN believes that ORP measurements are not sufficient to accurately quantify TRO levels.

The first BalPure ® 

### ORP probe confirms that there are residual oxidants in the treated water being discharged from the ballast tank. In principle, this confirmation of oxidants translates to affirmation that there are no living organism s in the discharge. The ORP reading at the first probe is typically between 700 and 800 mV and is used as an indicator that residual oxidant is present. The second ORP probe measures the ORP value of the deballast stream after bisulfite has been added to the discharge piping. This ORP value is typically <200 mV (similar to natural water) and is used to control the addition of bisulfite solution to ensure complete neutralization of residual oxidants. The low ORP value is an indicator that the

residual oxidant has been neutralized.

It is important to note the data from land-based testing confirms that the TRO (as Cl 2 

### ) concentration is below detection levels post neutra lization with sodium bisulfite. This verifies that residual oxidant neutralization with sodium bisulfite at discharge was effective at all ballast discharges and ensures that the maximum allowable discharge concentration (MADC) of <0.20 mg/L TRO (as Cl 2 

### ), as recommended by the GESAMP-BWWG, is not exceeded (see section 11.1).

### MEPC 61/2/9 Annex, page 32

I:\MEPC\61\2-9.doc 

### With the mixing effect of the deballast water pump and the discharge pipe, the bisulfite will easily react with any free oxidants that may be pr esent. As a fail-safe measure, the BalPure ® 

### system is fitted with two redundant bisulfite metering pumps; one pump is the primary dosing pump and the second is an on-line ready spare.

In the unlikely event of an equipment failure, the neutralization process can also be operated manually to ensure that residual oxidants are neutralized during discharge. This is accomplished by the operator manually setting the bisulfite metering pump rate in the PLC. The delivery rate of bisulfite can be set based on the stoichiometric ratio of oxidant to neutralizing agent at 1:2 parts. Thus the sulfite metering pumps are set based on the maximum discharge ballast water flow rate and hypochlorite concentration.

8.1.2 Chemical storage and handling

The only chemical that will require onboard storage and handling is the neutralizing agent, sodium bisulfite. The only potential activities that may require "handling" of bisulfite is either system maintenance or chemical re-supply operations. During the previous evaluation undertaken for STDN's application dossier for Basic Approval (MEPC 60/2/9, section 8.1.3) the Group recognized all risk evaluations of the ship and personnel including consideration of the storage, handling, and application of sodium bisulfite as sufficient and considered that this BWMS will not pose unacceptable risk regarding the exposure to bisulfite and treated ballast water (MEPC 60/2/16, sections 7.1 and 7.2). No changes have been made in the full-scale operation of the BalPure ® 

### system since the submittal of STDN's application dossier for Basic Approval. Therefore the previous evaluations made by the Group remain valid.

8.1.3 Various procedures and management measures

Technicians and ship's crew will be sufficiently trained in procedures and management measures concerning fire, accidental release, marine environmental release, and controlled release according to methods outlined in STDN's application dossier for Basic Approval (MEPC 60/2/9, section 8.1.3). During the previous evaluation undertaken for STDN's application dossier for Basic Approval, the Group recognized all working principles of the

BalPure ® 

### system as sufficient and considered that this BWMS will not pose unacceptable risk to the health of the crew and the general public (MEPC 60/2/16, sections 7.1 and 7.2). No changes have been made in the full-scale operation of the BalPure ® 

### system since the submission of STDN's application dossier for Basic Approval. Therefore the previous evaluations made by the Group remain valid, and no change to procedures and management measures are presented in this dossier.

9 MATERIAL SAFETY DATA SHEETS (G9: 4.2.7)

Information on the hazard classifications of Active Substances and Relevant Chemicals was presented in sections 9.1, 9.2 and 9.3 of STDN's application dossier for Basic Approval (MEPC 60/2/9) and all Material Data Safety Sheet (MSDS) were provided. In this Final Approval dossier, all MSDSs, including the three additional DBPs (dibromochloroacetic acid, tribromoacetic acid, and 2,4,6-tribromophenol) that were measured in treated ballast water during land-based testing are provided in appendix A.4.

It is important to note that these DBPs may be formed in situ at low concentrations as a result of ballast water treatment. Concentrated solutions of these DBPs will never be transported or utilized on board ship. As such, typical MS DSs for these low level (μg/L range) substances do not accurately represent the potential hazards in treated ballast water. Determining the hazards for these substances at μg/L levels is not feasible when the MSDSs reflect hazards for much higher concentrations.

### MEPC 61/2/9 Annex, page 33

I:\MEPC\61\2-9.doc 

### 10 RISK CHARACTERIZATION AND ANALYSIS

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

Table 19: PBT Criteria Evaluation

Substance Persistence (P) Half-life: >60 Days in Marine Water (MW), or >40 Days in Fresh Water (FW), or >180 Days in Marine Sediment (MS), or >120 Days in Fresh Water Sediment (FWS) (YES or NO) Bioaccumulation (B) BCF>2,000 Log Kow ≥ 3

(YES or NO) Toxicity (T)
Chronic NOEC < 0.01 mg/L

(YES or NO)

Active Substances

Hypochlorous acid No <2 hours (EU RAR Sodium hypochlorite, 2007)

FW No Log Kow = -0.87 No
Lowest NOEC = 0.048 mg/L (Crustacean)

Hypobromous acid No <2 hours (No specific data located, based on hypochlorous acid)

FW No
BCF = 3.2 Log Kow =-0.78
Koc = 13.2 No
Lowest EC 50 = 1.0 mg/L (Algae)

Relevant Chemicals

Bromate No 15 days (EPI Suite, 2009) Water type not specified; Temperature = 25°C; No
BCF = 3.2 Log Kow = -4.6
Koc = 31.8 No
Lowest EC 50 = 13.6 mg/L (Algae)

2,4,6-Tribromophenol No 1.21 days (CICADS 66, 2005)

FW No
BCF = 83 - 513 Log Kow =3.89 Koc = 1,186 No
Lowest NOEC = 0.10 mg/L (Crustacean)

THMs

Chloroform No 0.25 days (Yang, 2001); Not expected to adsorb into sediment (HSDB/TOXNET 2009)

MW No
BCF = 2.9-10.35

Koc = 153-196 No
Lowest NOEC = 1.5 mg/L (Fish)

Bromoform No 0.3 days (EU RAR Sodium hypochlorite, 2007)

FW No
BCF = 14 Log Kow 2.4
Koc = 35 No
Lowest NOEC = 8.5 mg/L (Fish)

Dichlorobromomethane No 0.08 days (EU RAR Sodium hypochlorite, 2007)

FW No
BCF = 7 Log Kow = 2
Koc = 35-251 No
Lowest LC 50 = 67.4 mg/L (Fish)

Dibromochloromethane No 0.11 days (EU RAR Sodium hypochlorite, 2007)

FW No
BCF = 9

Koc = 84 No
Lowest LC 50 = 34mg/L (Fish)

HAAs

Bromochloroacetic acid No 2.7 days (Hashimoto et al., 1998); Not expected to adsorb to suspended solids or sediment. (HSDB/TOXNET 2009) FW; Temperature = 20°C No
BCF = 3.2 Log Kow = 0.61

Koc = 1.9 Data not located.

Monochloroacetic acid No 3.58 Days (Hanson et al., 2002) FW; Temperature = 18.7- 23.8°C; pH = 7.7-8; DO= 92-11.3 mg/L; Alkalinity = 158-171 mg/L No
BCF = 3.2 Log Kow = 0.22
Koc = 31 No
Lowest NOEC = 32 mg/L (Crustacean)

Monobromoacetic acid No 3.2 days (Hashimoto et al., 1998); Not expected to adsorb to sediment. (HSDB/TOXNET 2009) FW; Temperature 20°C No
BCF = 3.2 Log Kow = 0.41
Koc = 39.8 No
Lowest NOEC = 1.4 mg/L (Algae)

### MEPC 61/2/9 Annex, page 34

I:\MEPC\61\2-9.doc Substance Persistence (P) Half-life: >60 Days in Marine Water (MW), or >40 Days in Fresh Water (FW), or >180 Days in Marine Sediment (MS), or >120 Days in Fresh Water Sediment (FWS) (YES or NO) Bioaccumulation (B) BCF>2,000 Log Kow ≥ 3

(YES or NO) Toxicity (T)
Chronic NOEC < 0.01 mg/L

(YES or NO)

Dichloroacetic acid No 5.4 days (Hashimoto et al., 1998) FW; Temperature 20°C No
BCF = 0.3 Log Kow = 0.92

Koc = 75 No
Lowest EC 50 = 23 mg/L (Crustacean)

Dibromochloroacetic acid No 3.67 days (Hashimoto et al., 1998) FW; Temperature 20°C No
BCF = 3.16 Log Kow = 1.62
Loc = 3.23 Data not located.

Dibromoacetic acid No 3.2 days (Hashimoto et al., 1998) FW; Temperature 20°C No
BCF = 0.17

Koc = 1.5 No
Lowest LC 50 = 69 mg/L (Fish)

Tribromoacetic acid No 4.2 days (Hashimoto et al., 1998) FW; Temperature 20°C No
BCF = 0.63

Koc = 5.3 Data not located.

Trichloroacetic acid No 14.37 days (Ellis et al. , 2001) FW; Temperature 20°C No
BCF = 0.1-1.7 Log Kow = 1.33
Koc = 130 No
Lowest NOEC = 100 mg/L (Algae)

Other Chemicals

Sodium bisulfite No 0.000747 days (Yan et al. , 2007) Salinity not specified; Temperature = 25°C; pH = 4; DO = 7.86 mg/L No
BCF = 3.2 Log Kow = -6.85
Koc = 2.21 No
Lowest LC 50 = 81 mg/L (Crustacean)



### Based on an evaluation of the available data presented in the Table, none of the substances

meet all three criteria to be considered as PBT substances.

10.1.1 Persistence (G9: 5.1.1.1)

Using the half-life criteria specified in Procedure (G9) (resolution MEPC.169(57)) of more than 40 days in fresh water, 60 days in marine water, marine sediment persistence more than 180 days, or fresh water sediment persistence greater than 120 days, an evaluation of the environmental persistence data for Active Substances, Relevant Chemicals, and other chemicals indicates that none of the substances are likely to be persistent in the

environment.

10.1.2 Bioaccumulation (G9: 5.1.1.2)

Using the criteria specified in Procedure (G9) (resolution MEPC.169(57)) of either BCF >2000 or Log Kow ≥ 3, an evaluation of the available data for Active Substances, Relevant Chemicals, and other chemicals indicates that the substances have low potential for bioaccumulation. Although 2,4,6-tribromophenol has a reported Log Kow of 3.89 (OECD, 2003) which is slightly above 3, the BCF is well below the criteria of 2000.

10.1.3 Toxicity tests (G9: 5.1.2.3)

Due to the limited availability of chronic aquatic toxicity data for some substances, the evaluation for toxicity was based on all available data. In some cases, acute endpoint data was utilized when available. For substances where no toxicity data points could be located, the data with respect to the other two PBT criteria is available and therefore, a PBT

determination can still be made.

### MEPC 61/2/9 Annex, page 35

I:\MEPC\61\2-9.doc 

### With the exception of substances having limited toxicity data, all other substances did not have chronic NOEC or E(L)C 50 

### values <0.01 mg/L. Therefore, the criterion to be considered

a toxic substance is not met.

11 EVALUATION OF THE TREATED BALLAST WATER (G9: 5.2)

Numerous studies have been conducted on the BalPure ® 

### system to evaluate various aspects of treated/neutralized water. In addition to the aquatic ecotoxicity data presented in section 3, data on TRO (as Cl 2 

### ), water quality parameters (e.g., salinity, pH, particulate organic carbon (POC), dissolved organic carbon (DOC), tota l suspended solids (TSS)), and disinfection by-products (DBPs) have been measured and recorded. Treated ballast water samples were collected immediately after neutralization at discharge. Samples were stored in proper sample containers at 4°C and transported to the designated lab within 24 hours of collection. Analysis of the samples occurred within the time specified under standard laboratory procedures.

11.1 Total Residual Oxidants

During testing of the BalPure ® 

### system conducted at the NIOZ land-based test ing facility in 2009, hypochlorite treatment was applied and TRO (as Cl 2 

### ) was measured at different time intervals after treatment. TRO (as Cl 2 

### ) was evaluated immediately after treatment (T0), 1 day after treatment (T1), 5 days after treatment (T5), and after neutralization on day 5 (post neutralization). The average TRO (as Cl 2 

### ) at each time interval for 6 low salinity test cycles and 6 high salinity test cycles are shown below in Table 20.

Table 20: Average Oxidant Values (mg/L) in Treated Ballast Water

Test Cycle

Salinity BalPure ®

Treatment Dose (Set Point) TRO (as Cl 2 ) @ T0 TRO (as Cl 2 ) @ T1 TRO (as Cl 2 ) @ T5 TRO (as Cl 2 ) Post

Neutralization

Low Salinity (23.68 PSU) 14.83 14.80 7.19 4.46 Not Detected

High Salinity (33.90 PSU) 13.17 12.36 4.97 2.98 Not Detected

Not Detected = <0.02 mg/L (Hach Method 8167)



### The data indicate that the applied hypochlorite treatment dose is confirmed following treatment by the TRO (as Cl 2 

### ) measurement at T0. As expected, the TRO (as Cl 2 

### ) concentration decayed quickly (TRO (as Cl 2 

### ) at T1) following treatment, and then more slowly after the demand of the water was met (TRO (as Cl 2 

### ) at T5). Lastly, the data confirm that the TRO (as Cl 2 

### ) concentration is below detection levels post neutralization with sodium bisulfite. This verifies that residual oxidant neutralization with sodium bisulfite at discharge was effective at all ballast discharges and ensures that the maximum allowable discharge concentration (MADC) of <0.20 mg/L TRO (as Cl 2 

### ), as recommended by the GESAMP-BWWG, is not exceeded. Also, the features of the BalPure ® 

### system pertaining to neutralization and ORP control (section 8.1.1.2) ensure sodium bisulfite addition for effective neutralization.

11.2 Water quality parameters

Water quality data was collected by the researchers at NIOZ during testing of the BalPure ®


### system in 2009. Land-based tests were done using natural waters taken from the Wadden Sea, with minimal amendments to alter water quality. Variation in water quality is caused by tidal and wind influences, which results in variable concentrations of TSS and POC. The average values for brackish water samples (low salinity) and marine water samples (high salinity) are presented in Table 21 below. Data is as provided to STDN by NIOZ.

### MEPC 61/2/9 Annex, page 36

I:\MEPC\61\2-9.doc 

### Table 21: Water Quality Data

Parameter Control Treatment

Brackish Water (low salinity)

T0 T5 T0 T5

pH 8.33 8.25 8.52 7.90

Temperature (  ̊ C) 11.45 11.35 11.05 11.23

Salinity (PSU) 24.05 24.05 23.68 23.68

POC (mg/L) 16.34 25.79 15.31 5.62

DOC (mg/L) 2.85 2.69 3.00 3.50

TOC (mg/L)* 19.19 28.48 18.31 9.12

TSS (mg/L) 46.83 16.20 41.91 12.58

DO (%) 111.05 91.87 138.08 119.60

Marine Water (high salinity)

T0 T5 T0 T5

pH 8.10 7.92 8.33 7.50

Temperature (  ̊ C) 14.56 14.30 14.66 14.48

Salinity (PSU) 33.40 33.40 33.90 33.90

POC (mg/L) 7.63 4.96 8.07 3.68

DOC (mg/L) 3.04 2.77 3.31 3.69

TOC (mg/L)* 10.67 7.73 11.38 7.37

TSS (mg/L) 18.55 10.66 19.60 8.38

DO (%) 92.25 68.11 126.94 106.02

* TOC = DOC +POC



### The physical and chemical properties of treated ballast water were provided in STDN's application dossier for Basic Approval (section 6 and Table 21).

11.3 Chemical analysis of disinfection by-products in treated ballast water

During land-based testing of the full commercial BalPure ® 

### system conducted at NIOZ in 2009, treated ballast water discharge was evaluated for disinfection by-products (DBPs). DBP concentrations from three low salinity and three high salinity test cycles were quantified. During each test cycle, samples were collected on Day 1 (24 hours post-treatment) and Day 5 (5 days post-treatment), resulting in 6 separate analyses for each water type. All samples were neutralized at discharge to ensure that the data represent full-scale employment (hypochlorite treatment + sodium bisulfite neutralization) of the ballast water system.

Table 22 presents DBP data for samples collected on Day 1 (24 hours post-treatment) for low salinity (23.68 PSU) and high salinity (33.90 PSU) test cycles. Table 23 presents DBP data for samples collected on Day 5 (5 days post-treatment) for low salinity (23.68 PSU) and high-salinity (33.90 PSU) test cycles.

Table 22: Post-Treatment Disinfection By-product Concentrations – Day 1

(Table 22 provided in confidential dossier.)

### MEPC 61/2/9 Annex, page 37

I:\MEPC\61\2-9.doc 

### Table 23: Post-Treatment Disinfection By-product Concentrations – Day 5

(Table 23 provided in confidential dossier.)

For THM analysis, three of the four substances tested in both high and low salinity cycles indicate that bromoform, DBCM and DCBM had measurable concentrations in treated/ neutralized discharge. Chloroform was not detected in any sample analysed. Low levels (0.15-2.7 μg/L) of bromoform were also present in untreated (control) water for both high and low salinity test cycles. As previously mentioned in section 2.3.1, bromoform is a chemical naturally produced by many algal species such as Macrocystis pyrifera and Corallina pilulifera (HSDB/TOXNET Tribromomethane, 2009; Goodwin et al., 1997; Ohsawa et al. , 2001).

For HAA analysis, MBAA, DBAA, TBAA, MCAA, DBCAA and BCAA had measurable concentrations in low salinity test cycles. In high salinity test cycles, MBAA, DBAA, TBAA, DCAA, DBCAA and BCAA were present with measurable concentrations.

In brackish water test cycles, 2,4,6-TBP had measurable concentrations in treated water (0.67-1.3 μg/L), as well as in untreated (control) water (0.44-1.80 μg/L). The background concentration was consistently significant (see discussion on modelling 2,4,6 TBP; section 11.8.2). The substance, 2,4,6-TBP, has been documented to occur in natural environments, either as a pollutant from anthr opogenic sources (wood industry, antifungal use) or from natural production by marine benthic organisms (OECD SIDS, 2003). Therefore, the presence of 2,4,6-TBP in control samples is consistent with the findings of other studies.

Sodium bisulfite is added in excess to ensure complete neutralization of remaining oxidants in ballast water discharge. In one sample, a maximum concentration of 8 mg/L sulfite ion was measured in ballast water discharge. The median concentration measured for all samples was 5 mg/L. Bisulfite was measured immediately after injection into the discharge pipe to ensure that an excess is present, which the data confirms. The bisulfite concentration ranges in low and high salinity test cycles was 2.0-8.0 mg/L and 2.0-3.0 mg/L, respectively. As discussed above in section 2.4.1, bisulfite is converted to bisulfate, and ultimately to sulfate ion during chemical reduction. Both the control and treated waters were analysed to verify that the excess of bisulfite does not significantly increase the sulfate ion.

The data in Tables 22 and 23 show the difference between the measured sulfate ion in control and treated samples is insignificant (<10%). Considering the typical concentration of sulfate ion in natural waters, the increase of sulfate ion in ballast water discharge is not considered environmentally relev ant. GESAMP-BWWG agrees that sulfate ion is ubiquitous in the marine environment and considered that the discharge or environmental concentrations of sodium bisulfite should not pose unacceptable environmental risks (MEPC 60/2/16, section 3.1.1.4).

As discussed in section 5.4, formation of DBPs is dependent upon several variables such as Active Substance dose, contact time, pH, and organic matter content. Data from the

BalPure ® 

### discharge reflects those trends. For instance, the highest THM and HAA formation occurred in the brackish water treatment where the hypochlorite dose, organic matter, and suspended solids were the highest. Similarly, the lowest THM and HAA formation occurred in the seawater study where the hypochlorite dose, organic matter and suspended solids

were at lower levels.

### MEPC 61/2/9 Annex, page 38

I:\MEPC\61\2-9.doc 

### 11.4 Ecotoxicity testing of treated ballast water, land-based testing

Samples of water treated with the BalPure ® 

### system during land-based testing at NIOZ were evaluated by Grontmij|AquaSense ( The Netherlands) and Chemex Environmental International Ltd. (UK). Ecotoxicity data is presented in section 3 and Tables 3 and 5. Toxicity tests were conducted with six taxonomic groups including bacteria, algae, crustaceans, rotifers, mollusks and fish in two water types; low salinity (23.68 PSU) and high salinity (33.90 PSU). The samples for ecotoxicity testing were collected on Day 1 and on Day 5 after ballast water treatment/neutralization. All tests were performed according to laboratory protocols based on internati onally recognized ISO, OECD, ASTM, and Parcom/OSPAR guidelines. Documentation of quality assurance for Grontmij|AquaSense and Chemex Environmental International Ltd. are included in appendix A.6.

The acute testing data indicate that 100% whole effluent did not have toxic effects on five of the six species tested (Table 3). One of four acute tests with the crustacean, Acartia tonsa, in the low salinity sample collected 24 hours after treatment (Day 1) indicated there was a moderate effect in the two highest test concentrations (100% and 32% sample). This is reflected by a NOEC of 18% volume (Grontmij|AquaSense, 2009).

It is important to note that during tests with Acartia moderate effects were also observed in a control (untreated NIOZ harbour water) sample (EC 20 

### of 58% sample) (Grontmij|AquaSense, 2009). A possible explanation for the moderate toxic effect in the treated and control samples is the presence of Phaeocystis, an algal species known to be abundant in the NIOZ harbour and to excrete allelochemicals. Although not a highly toxic algal species, the massive blooms often result in ecosystem effects. Residual grazing deterrents and growth retarding compounds were likely to be the main cause of the effects on

Acartia tonsa in the control and treated ballast water test cycles (Veldhuis and Kools, 2009). Phaeocystis was present in the NIOZ harbour during the whole season of testing but was particularly abundant during the first low salinity test cycles (Veldhuis and Kools, 2009), which corresponds with when effects were observed in the Acartia tests.

All other acute (Table 3) and chronic (Table 5) tests with Acartia, as well as the five other species tested, demonstrate that 100% whole effluent sample had no toxic effect, indicating that the NOEC of 18% (Table 3) is an outlying data point.

11.5 Determination of holding time

Because the BalPure ® 

### system employs an oxidant neutraliz ation step at discharge, there is no specified holding time required before treated water can be safely discharged to the environment. Using ORP technology (discussed in section 8.1.1.2) sodium bisulfite can be added to the ballast water discharge line at the concentration needed to ensure that all residual oxidants are neutralized, regardless of when deballasting needs to occur. The neutralization reaction between sodium bisulfite and TRO (as Cl 2 

### ) is extremely quick and occurs well before water is discharged from the ballast tank.

Therefore, the holding time that treated ballast water needs to be retained is determined by the amount of contact time required to properly disinf ect and inactivate AIS. Studies performed at the University of Washington determined that at low (<2 mg/L) TOC concentrations 98-100% of organisms were inactivated 5 hours after hypochlorite treatments of 2.95-3.71 mg/L (Herwig et al. , 2006). Studies performed at the Naval Research Laboratory determined BalPure ® 

### hypochlorite treatments of 14-16 mg/L effectively inactivated >99% of organisms 24 hours after treatment in seawater with 10 mg/L TOC (NRL, 2007). These studies indicate that even if a ship had to discharge treated ballast water shortly after hypochlorite treatment, the number of live organisms would be very limited and no aquatic toxicity could be expected from neutralized discharge.

### MEPC 61/2/9 Annex, page 39

I:\MEPC\61\2-9.doc 

### 11.6 Reaction with organic matter

As discussed in STDN's application dossier for Basic Approval (MEPC 60/2/9) and in section 5.4, chlorine-based water disinfection c an result in the formation of THMs, HAAs or other DBPs. The concentration of these DBPs resulting from disinfection is based on the Active Substance dose as well as the parameters of the water being treated (e.g., organic matter, pH, temperature), with the amount of organic matter being of significant influence. Lower organic matter levels will reduce the amount of DBPs formed. The BalPure ® 

### system filters incoming ballast water, which will reduce the amount of organic matter in treated water, and thereby, the DBPs formed during disinfection. The levels of DBPs in treated/neutralized ballast water are presented in section 11.3, Tables 22 and 23.

Because TRO (as Cl 2 

### ) is neutralized during discharge, and also considering that DBPs are present in the μg/L range in ballast water discharge, no additional reactions with organic matter are expected to occur once ballast water is released into the environment.

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

Table 16 above includes degradation data for substances not previously analysed for or presented in STDN's application dossier for Basic Approval (MEPC 60/2/9) and which were measured in treated/neutralized ballast water during land-based testing. Degradation information on all previously measured substa nces was presented in the Basic Approval dossier (MEPC 60/2/9, Table 16).

The data indicate that both biotic and abiotic modes of degradation are possible for 2,4,6-TBP, and degradation in anaerobic sediments is rapid (half-life of ~4 days (CICADS 66, (2005)). In an activated sludge study, 2,4,6-TBP reached 49% of the biological oxygen demand (BOD) in 28 days (CICADS 66, 2005). However, in 3-day biodegradation tests in river water, 2,4,6-TBP (10 mg/L) was degraded by 82% (CICADS 66, 2005). Based on the low concentrations (maximum = 1.3 μg/L) of 2,4,6-TBP present in ballast water discharge and the rapid degradation of 2,4,6-TBP documented in water and sediment, there is low potential for persistence and impacts to the aquatic environment from 2,4,6-TBP.

Degradation data for DBCAA and TBAA is limited. However, the stability of HAAs in water was evaluated in Tokyo Bay (Hashimoto, et al , 1998). In river water, DBCAA (20 μg/L) degraded to <0.069 μg/L after a 30-day incubation. Similarly, TBAA (10 μg/L) degraded to <0.070 μg/L after a 30-day incubation. The studies also showed that abiotic and biotic degradation occurred for HAAs. This was demonstrated by samples that were allowed to degrade with and without microbial inhibitors. Prior work with HAA stability also indicates that bacterial enzymes (haloacid dehalogenases) decompose HAAs (Hashimoto et al., 1998). As such, these substances are not expected to persist in the environment.

11.8 Prediction of discharge and environmental concentrations (G9: 5.3.8)

To determine the predicted environmental concentrations (PECs) of substances associated
with STDN BalPure ® 

### system, the MAMPEC modelling program was utilized. Deltares, located in the Netherlands, developed the MAMPEC model and was commissioned by STDN to derive PEC values. Appropriate emission scenarios were developed in consultation with Deltares' hydrodynamic modelling experts. Due to Deltares' continued research and development of the MAMPEC model, it was dete rmined that a research version of MAMPEC was the best to utilize for this assessment. This research version, not currently available on the internet, incorporates the latest developmen ts and is based on the last officially released MAMPEC version (2.5.04) (Deltares, 2010).

### MEPC 61/2/9 Annex, page 40

I:\MEPC\61\2-9.doc 

### 11.8.1 Hydrodynamic modelling approach

It is important to note that the MAMPEC model was designed as a rapid assessment tool to evaluate the continuous leaching of anti-fouli ng products from ships' hulls. To determine PEC values, MAMPEC employs a "steady state" approach, which implies that an equilibrium
concentration of a substance in a harbour is calculated under constant environmental conditions as a result of continuous and constant emission (Deltares, 2010). This is very different from the intermittent and non-continuous nature of ballast water discharges. Therefore, the steady state approach in MAMPEC simulations likely overestimates PEC values and provides a highly conservative, worst-case scenario.

In an effort to predict conservative environmental concentrations of substances present in

BalPure ® 

### treated/neutralized ballast water discharge, two different environmental schematizations were employed. These two scenarios are labelled "Environment A" and

"Environment B".

Environment A applied a simulation environment defined by the "OECD-EU commercial harbour" configuration which is the recommended scenario for risk assessment of antifoulants in all OECD regulatory frameworks. The "O ECD-EU commercial harbour" is a downsized version of the whole Port of Rotterdam being four times smaller than the Rotterdam harbour,
with a surface area of 5 km 2 

### (Deltares, 2010). To determine the amount of ballast water discharge in the harbour, the ballast water discharge estimated by Van Niekerk (2008) was used. According to the Van Niekerk study, a monthly estimate of ballast water discharge

amounted to 2.76 million m 3 

### for the entire Port of Rotterdam. The flow rate specified in the MAMPEC model was derived using the 2.76 million m 3 

### ballast water discharge volume, which equalled 1.10 m 3 

### /s. Given that the "OECD-EU commercial harbour" configuration is four times smaller than the whole Port of Rotterdam, using this ballast water discharge flow rate representative of the entire Rotterdam harbour constitutes a highly conservative worst case scenario. Environment A also used the standard exchange flow of 5.1x10 7 

### m 3 

### per tidal cycle, which equals 68% of the total harbour water volume.

Environment B modelled substances present in BalPure ® 

### treated/neutralized ballast water discharge using the same "OECD-EU commercial harbour" configuration and ballast discharge flow rate as Environment A, with the exception that a lower tidal exchange flow

rate was used. This alternative environment had smaller density driven water exchange in the harbour. The harbour water exchange resulting from density differences was assigned a value of 0.02 kg/m 3 

### in Environment B compared to the value of 0.4 kg/m 3 

### assigned in Environment A. The exchange flow rate for Environment B was 2.1x10 7 

### m 3 

### per tidal cycle, which equals only 28% of the total harbour water volume. Therefore, the Environment B emission scenario and the resulting PEC values can be considered extremely conservative. The harbour is smaller, the amount of water exchange (flushing) is greatly reduced, yet the ballast water discharge rate is based on statistics for the whole Port of Rotterdam.

11.8.2 Determination of substance concentrations and decay rates for modelling input

Due to the oxidant neutralization step during ballast water discharge, the TRO (as Cl 2 

### ) in treated water discharge will not be present in measurable concentrations. Therefore, the discharge and predicted environmental concentration (PEC) for TRO (as Cl 2 

### ) is 0 mg/L.

The relevant substance concentrations used for MAMPEC modelling were based on analysis of treated/neutralized ballast water samples drawn from the full-scale land-based test set-up
of the BalPure ® 

### system. For the purposes of modelling, the highest median concentration for each Relevant Chemical with a measurable concentration (as presented in the Table 24), regardless of the water type (high or low salinity water), was entered into the model.

### MEPC 61/2/9 Annex, page 41

I:\MEPC\61\2-9.doc 

### This approach ensured a representative evaluation of potential environmental risk as a result of DBPs in ballast water discharge.

For each substance analysed, the median concentration was calculated by using all available data to derive the most representative conc entration for each salinity. For example, six separate analyses for bromoform were performed in the low salinity test cycles, and the median result of these 6 data points was derived. Because the data were not normally distributed and the data set was relatively small (n<10) for each substance, median values are the most representative and appropriate. Additionally, due to the layers of conservatism already built into the environmental risk assess ment (discussed in section 12.3) the use of median values allowed for a more realistic assessment of discharge DBP concentrations. The median result, as well as the minimum and maximum concentration, for each Relevant Chemical is presented in Table 24 below.

In the case of TBAA, MCAA (low salinity cycles) and DCAA (high salinity cycles) the average concentrations, rather than medians, were calculated and used for MAMPEC modelling. This was done because a median calculation would not have been representative of all data points. For these substances, the average is a more representative result. The results are presented in Table 24 below.

Residual sodium bisulfite present in neutralized discharge was also measured; the data is presented in Table 24 below.

Table 24: Median Disinfection By-product Concentrations

(Table 24 provided in confidential dossier.)

As discussed in sections 2.3.2 and 11.3, 2,4,6-TBP has been documented to occur naturally. The median 2,4,6-TBP concentration present in control samples was significant when compared to the median concentration in treated water samples. The difference between background 2,4,6-TBP levels in the control water and treated water is 0.21 μg/L. As such, the concentration modelled in MAMPEC was derived by subtracting the median control concentration from the median treated ballast water concentration (Table 24). This approach achieves a more realistic 2,4,6-TBP concentration in ballast water discharge as a result of

the BalPure ® 

### system and excludes 2,4,6-TBP apparently present in natural water.

As presented in section 2.3.1 above, bromofor m is also a naturally produced chemical. Because median bromoform concentrations in control samples were at low levels and not considered significant when compared to treated sample median concentrations, the control concentration was not subtracted from the treated ballast water samples for the purposes of MAMPEC modelling.

Sodium bisulfite is added to ballast water discharge at an excess (median = 5 mg/L; maximum = 8 mg/L) to ensure that all residual oxidants have been reacted (Tables 23 and 24). As such, ballast water discharge may contain sodium bisulfite. To demonstrate that any excess sodium bisulfite that may be present in ballast water discharge does not present environmental risk, the median bisulfite concentration measured was evaluated with MAMPEC.

Table 25 below summarizes the Relevant Chemical concentrations and the associated half-lives in water used for MAMPEC modelling.

### MEPC 61/2/9 Annex, page 42

I:\MEPC\61\2-9.doc



### Table 25: Summary of Relevant Chemical Concentration and Half-life for Modelling

Substance Highest Median Discharge
Concentration Half-life in

Water Reference/Comments

Disinfection By-products (DBPs)
Bromoform 500 μg/L 0.3 days EU RAR Sodium Hypochlorite (2007)

Dichlorobromomethane 0.98 μg/L 0.08 days EU RAR Sodium Hypochlorite (2007)

Dibromochloromethane 21 μg/L 0.11 days EU RAR Sodium Hypochlorite (2007)

Bromochloroacetic acid 13 μg/L 2.7 days Hashimoto et al. (1998)

Monochloroacetic acid 1. 08 μg/L 3.58 days Hanson et al. (2002)

Monobromoacetic acid 14.5 μg/L 3.2 days Hashimoto et al. (1998)

Dichloroacetic acid 1.15 μg/L 5.4 days Hashimoto et al. (1998)

Dibromoacetic acid 50 μg/ L 3.2 days Hashimoto et al. (1998)

Tribromoacetic acid 13.66 μg/L 1 4.2 days Hashimoto et al. (1998)

Dibromochloroacetic acid 8.8 μg/L 1 3.67 days Hashimoto et al. (1998)

2,4,6-Tribromophenol 0.21 μg/L 2 1.21 days CICADS 66 (2005)

Neutralization Chemical
Sodium bisulfite 5.0 mg/L 0.000747 days 3 Yan et al. ( 2007)

1 = average concentration. See sectio n 11.3 for calculation explanation.

2 = concentration in ballast water discharge afte r concentration in control sample subtracted.

3 = derived using a zero-order rate constant (Deltares, 2010).



### 11.8.3 Predicted Environmental Concentration results from MAMPEC modelling

The PEC values as a result of the two different MAMPEC modelling approaches used by Deltares are presented below. Table 26 includes the PEC values for both Environment A

and the more conservative Environment B.

Table 26: PEC Summary for Environment A and Environment B

Substance PEC (μg/L)

Environment A PEC (μg/L)

Environment B

Bromoform 0.3190 0.3810

Dichlorobromomethane 0.0002 0.0002

Dibromochloromethane 0.0057 0.0059

Total THMs 0.3249 0.3871

Bromochloroacetic acid 0.0236 0.0646

Monochloroacetic acid 0.0021 0.0064

Monobromoacetic acid 0.0272 0.0799

Dichloroacetic acid 0.0023 0.0084

Dibromoacetic acid 0.0939 0.2757

Tribromoacetic acid 0.0269 0.0877

Dibromochloroacetic acid 0.0169 0.0525 2,4,6-Tribromophenol 0.0003 0.0006

Sodium bisulfite 0.0133 0.0133



### The simulated environmental concentrations primarily depend on three aspects of the modelling input: the substance emission (i.e . discharge concentration), the substance characteristics (i.e. half-life), and the environmental conditions (harbour configuration, flushing, etc.). For instance, the role of substance decay rates is evident when evaluating TBAA and DBCM (Tables 25 and 26). The emissi ons for these two substances are in the same order, but as the data indicate, Environment A PEC values differ by an order of magnitude due to the difference in the decay rates of these substances (Deltares, 2010).

### MEPC 61/2/9 Annex, page 43

I:\MEPC\61\2-9.doc 

### The effect of varying environmental conditions can be seen when comparing the PEC values for Environment A with Environment B. The "reduced flushing" in Environment B produces larger PEC values for most substances, primarily for those with slower decay rates. This is because removal of these substances from a harbour is more dependent upon flushing, and flushing is reduced in the Environment B simulation. For unstable substances with rapid decay rates, the reduced flushing in Environment B is less influential. This is because the substances decay rapidly and disappear before the effect of flushing can be realized (Deltares, 2010).

To ensure that the results obtained with the MAMPEC research version could be considered sufficiently conservative, Deltares also generated PEC values with the last officially released version of MAMPEC (version 2.5.04). Appendix B of the Deltares report provides PEC values generated with MAMPEC version 2.5.04. For t he most conservative environment in this assessment (Environment B), the simulations with the research version produced PEC values consistently higher than those obtained with version 2.5.04 (appendix B, Deltares, 2010). Therefore, the research version of MAMPEC used in this assessment of the BalPure ® 

### system can be considered more conservative (Environment B) and comparable to the standard
version of MAMPEC.

11.9 Effects on aquatic organisms

In this section, the available ecotoxicity data for each substance that had measurable concentrations in ballast water discharge is evaluated and appropriate Predicted No Effect Concentration (PNEC) values are derived. PNEC values for substances that were analysed for, but not found with measurable concentrations in treated/neutralized ballast water discharge, are not derived or considered. Tabl es 22 and 23 present the concentrations of substances measured in ballast water discharge.

A thorough literature review of available acute and chronic aquatic ecotoxicity data for the substances associated with the STDN system was conducted; the data are presented in Tables 2 and 4. However, the data set is limited for many of the substances. In some cases, data located in literature did not meet validity criteria and could only be used as supporting information. This resulted in incomplete data sets for fish, crustaceans, and algae that prevented individual PNEC derivation for all substances based on the guidance in the Methodology (23 May 2008 version) as well as the EU Technical Guidance Document on Risk Assessment (2003). Similar data gaps are also noted in other dossiers submitted for Procedure (G9) approval, suggesting that other literature searches have had similar findings.

When a complete valid data set was located in literature, and/or any supporting data could be identified, the reported toxicity values have been used for PNEC derivation. Where available data is limited, the PNEC derivat ion approach used in the European Union Risk Assessment Report (EU RAR) for Sodium Hypochlorite (2007) was followed.

Because the STDN system employs a neutralization step during deballasting, no measureable concentration of TRO (as Cl 2 

### ) is present in ballast water discharge. As TRO (as Cl 2 

### ) includes HOCl/OCl
- 

### and HOBr/OBr
- 

### these substances are therefore not considered relevant with respect to PNEC derivation.

A PNEC value of 2.0 μg/L for 2,4,6-TBP was derived based on a complete chronic aquatic ecotoxicity data set. The lowest chronic effect (NOEC) concentration located was 0.10 mg/L, and because the chronic and acute data set was complete an assessment factor of 50 was applied. This assessment factor and PNEC value is also reported in the CICADS 66 (2005) document for 2,4,6-TBP.

### MEPC 61/2/9 Annex, page 44

I:\MEPC\61\2-9.doc 

### With respect to THMs, a complete valid acute toxicity data set was available for bromoform, and two chronic endpoints (one fish, one alga) were available as supporting information. Using the lowest acute effect concentration (12.3 mg/L) and an assessment factor of 1000, results in a bromoform PNEC of 12.3 μg/L. The data sets for dibromochloromethane (DBCM) and dichlorobromomethane (DCBM) were incomplete. One valid acute endpoint for fish and
one acute test with a ciliate was located for DBCM. No chronic studies for DBCM were located. For DCBM, two acute endpoint studies with fish and one additional acute test with a ciliate were located. No chronic endpoint studies for DCBM were located. It is beyond the scope of the application process under Procedure (G9) to conduct chemical-specific testing with these substances on a variety of organisms to complete the data set available in open literature. This is particularly true considering that whole effluent toxicity (WET) testing results of the ballast water discharge are available. Therefore, as an alternative to having
PNEC values that are non-derivable for DBCM and DCBM, the PNEC derivation approach for THMs used in the EU RAR for Sodium Hypochlorite (2007) was utilized. For chloroform, the EU RAR references an aquatic PNEC of 146 μg/L. The EU RAR presents that the data collected in connection with an assessment for seawater chlorination "... suggest that the ecotoxicities of the brominated THMs are not markedly different from chloroform" (EU RAR, Sodium Hypochlorite, 2007). The EU RAR concludes that for the purposes of a broad assessment, THMs can be regarded as having similar toxicities and applies the
chloroform PNEC to total trihalomethanes. T herefore, utilizing the EU RAR suggested PNEC value of 146 μg/L for total THMs ensures that all THMs are considered, even in cases where toxicity data is limited and individual PNEC values cannot be derived. To maintain a conservative approach, the lower PNEC value for bromoform (12.3 μg/L) derived from the

available data can still be us ed for PEC/PNEC ratio evaluation.

For all HAAs, the database is incomplete with respect to chronic ecotoxicity endpoints. With the exception one HAA, monobromoacetic acid (MBAA), the acute aquatic toxicity database is also incomplete and did not allow for direct PNEC calculation for each individual HAA. Again, it is beyond the scope of the application process under Procedure (G9) to conduct the extensive amount of toxicity testing that would be required to complete the HAA data set. This is particularly true considering that whole effluent toxicity (WET) testing results of ballast water discharge are available. Therefore, the approach utilized in the Sodium Hypochlorite EU RAR (2007) for PNEC derivati on of HAAs was utiliz ed. That is, the EU RAR considered it

"... conservative to treat all haloacetic acids simplistically as being TCAA ..." in regards to PNECs and all HAAs could be considered to have a PNEC of 0.85 μg/L. Since this PNEC is far lower than the PNEC of 500 μg/L that would be derived for TCAA based on the data found in literature (acute data set in Table 2 and assessment factor of 1000), 0.85 μg/L is very protective and seems to be a reasonable approach for this assessment.

For sodium bisulfite, the available aquatic toxicity data in literature was also limited. No chronic endpoint studies were located, which is likely due to the rapid degradation (minutes time scale) of sodium bisulfite. Two acute endpoints for fish were located along with three acute endpoints for crustaceans. Si nce the submission of the Basic Approval dossier, STDN commissioned a study (Nautilus, 2009) to determine the ecotoxicity of sodium bisulfite to algae to complete the data set. Evaluating the completed data set, the lowest acute effect was 81 mg/L sodium bisulfite ( Daphnia magna ). Using an assessment factor of 1000, a PNEC value of 81 μg/L was derived. Table 27 below provides a summary of the
PNEC values derived.

### MEPC 61/2/9 Annex, page 45

I:\MEPC\61\2-9.doc 

### Table 27: PNEC Derivation Summary

Substance Lowest Effect
Concentration (mg/L) Assessment
Factor PNEC Value (μg/L) Reference/Comments

Relevant Chemicals

2,4,6-Tribromophenol 0.1 50 2.0 21-day NOEC for Daphnia

magna ; supported in CICADS 66 (2005)

THMs

Bromoform 12.3 1000 12.3 / 146 146 μg/L to be used as PNEC
for Total THMs

Dibromochloromethane (DBCM) Insufficient Data

Located -- Not Derivable Use EU Sodium Hypochlorite RAR suggested PNEC for

Total THMs

Dichlorobromomethane (DCBM) Insufficient Data

Located -- Not Derivable Use EU Sodium Hypochlorite RAR suggested PNEC for

Total THMs

Total THMs -- -- 146 Based on EU Sodium Hypochlorite RAR suggested
PNEC for Total THMs

HAAs

Bromochloroacetic acid Insufficient Data

Located -- 0.85 Based on EU Sodium Hypochlorite RAR suggested
PNEC for HAAs

Monochloroacetic acid Insufficient Data

Located -- 0.85 Based on EU Sodium Hypochlorite RAR suggested
PNEC for HAAs

Dichloroacetic acid Insufficient Data

Located -- 0.85 Based on EU Sodium Hypochlorite RAR suggested
PNEC for HAAs

Dibromochloroacetic

acid Insufficient Data

Located -- 0.85 Based on EU Sodium Hypochlorite RAR suggested
PNEC for HAAs

Monobromoacetic acid Insufficient Data

Located -- 0.85 Based on EU Sodium Hypochlorite RAR suggested
PNEC for HAAs

Dibromoacetic acid Insufficient Data

Located -- 0.85 Based on EU Sodium Hypochlorite RAR suggested
PNEC for HAAs

Tribromoacetic acid Insufficient Data

Located -- 0.85 Based on EU Sodium Hypochlorite RAR suggested
PNEC for HAAs

Other Chemicals

Sodium bisulfite 81 1000 81 Based on lowest acute effect;

no chronic data available.



### Utilizing the PEC values obtained with MAMPEC modelling for two different environmental configurations and the PNEC values derived from available toxicity data enables calculation of PEC/PNEC ratios. The tables below show each PEC and PNEC value and the resulting
ratios for the two different emission scenarios modelled with MAMPEC.

### MEPC 61/2/9 Annex, page 46

I:\MEPC\61\2-9.doc 

### Table 28: PEC/PNEC Calculation for MAMPEC Environment A

Substance PEC μg/L (Environ. A) PNEC (μg/L) PEC/PNEC

Relevant Chemicals

2,4,6-Tribromophenol 0.0003 2.0 0.00015

THMs

Bromoform 0.3190 12.3 0.02593

Dichlorobromomethane 0.0002 Not Derivable --

Dibromochloromethane 0.0057 Not Derivable --

Total THMs 0.3249 146 0.00222

HAAs

Bromochloroacetic acid 0.0236 0.85 0.02776

Monochloroacetic acid 0.0020 0.85 0.00243

Monobromoacetic acid 0.0272 0.85 0.03200

Dichloroacetic acid 0.0023 0.85 0.00275

Dibromoacetic acid 0.0939 0.85 0.11047

Tribromoacetic acid 0.0269 0.85 0.03164

Dibromochloroacetic acid 0.0169 0.85 0.01988

Other Chemicals

Sodium bisulfite 0.0133 81 0.00016



### Table 29: PEC/PNEC Calculation for MAMPEC Environment B

Substance PEC μg/L (Environ. B) PNEC (μg/L) PEC/PNEC

Relevant Chemicals

2,4,6-Tribromophenol 0.0006 2.0 0.00029

THMs

Bromoform 0.3810 12.3 0.03097

Dichlorobromomethane 0.0002 Not Derivable --

Dibromochloromethane 0.0059 Not Derivable --

Total THMs 0.3871 146 0.00265

HAAs

Bromochloroacetic acid 0.0646 0.85 0.07600

Monochloroacetic acid 0.0063 0.85 0.00747

Monobromoacetic acid 0.0799 0.85 0.09400

Dichloroacetic acid 0.0084 0.85 0.00982

Dibromoacetic acid 0.2757 0.85 0.32435

Tribromoacetic acid 0.0877 0.85 0.10317

Dibromochloroacetic acid 0.0525 0.85 0.06176

Other Chemicals

Sodium bisulfite 0.0133 81 0.00016

### MEPC 61/2/9 Annex, page 47

I:\MEPC\61\2-9.doc 

### For both Environment A and B, the highest PEC/PNEC ratio result was for DBAA (0.11047 and 0.32435, respectively). All other ratios were well below 1, even when using PEC values derived from the very conservative Environment B. Therefore, the data indicate that all PEC/PNEC ratios are <1. According to section 7.3.2 of the Methodology (23 May 2008), when no aquatic toxicity of the ballast water discharge is found through direct testing, or the PEC/PNEC ratios are <1, no further assessment of direct toxic effects to the aquatic environment is necessary.

11.10 Assessment of potential for bioaccumulation

Based on the data presented in this Final Approval dossier, as well as in the Basic Approval dossier (MEPC 60/2/9) all of the substances associated with the BalPure ® 

### system have low BCFs (<2000), indicating that they are unlikely to bioaccumulate in aquatic organisms or present a significant food chain risk. With the exception of the THMs and 2,4,6-TBP, the Active Substances and Relevant Chemicals have very low log Kows, which indicates the compounds are hydrophilic. The THMs and 2,4,6-TBP, as would be expected, are moderately hydrophobic. However, none of the THM log Kow values estimated and/or

located in the literature are ≥ 3 and none of the BCFs are ≥ 2000 (Table 19). For 2,4,6-TBP, the reported log Kow is slightly above 3 (3 .89); however, the BCF is less than 2000. Therefore, bioaccumulation potential is low.

11.11 Effects on sediment

Based on the chemical and physical properties of all substances associated with the

BalPure ® 

### system presented in this Final Approval dossier, as well as in the Basic Approval dossier (MEPC 60/2/9), no effects on sediment are anticipated (sections 3.4 and 5.2). The only exception is 2,4,6-TBP with a Koc value of 1,186 L/kg (Table 6), which indicates a moderate potential for partitioning into sediment. When 2,4,6-TBP is released to water, 93% is expected to stay in the water compartment and 7% is transported to the sediment compartment (OECD SIDS, 2003). This substance is also reported to dehalogenate rapidly in anaerobic sediments, with a reported half-life of approximately 4 days (CICADS 66, 2005). This is much more rapid than the sediment persistence criteria of 180 days in marine sediment or 120 days in fresh water sediment (Table 19 and the Methodology, section 6.1.4). Considering the low concentration of 2,4,6-TBP in ballast water discharge, a moderate potential for sediment adsorption, and the rapid sediment degradation, no effects on sediment are expected as a result of the BalPure ® 

### system.

11.12 Effects assessment

The data presented in this Final Approval dossier , as well as in the Basic Approval dossier (MEPC 60/2/9), for the substances associated with the BalPure ® 

### system indicate that there is a low potential for bioaccumulation and persistence in the aquatic environment, and moderate potential for sediment adsorption for one substance (2,4,6 TBP). Moderate sediment adsorption for 2,4,6-TBP poses low potential risk because the 2,4,6-TBP median concentration discharged by the BalPure ® 

### system was only slightly more (0.21 μg/L) than the environmental background level measured in the control (untreated water) samples. Further, 2,4,6-TBP is readily biodegradable in anaerobic sediment (Table 16) and the 2,4,6-TBP concentration in ballast water discharge is well below the lowest effect level for Daphnia magna (21-day NOEC of 0.10 mg/L, Table 4).

No effects or risks in the form of secondary (f ood chain) poisoning or to sediment species are anticipated. The information reviewed for degradation and bioaccumulation of the substances

related to the BalPure ® 

### system suggest that potential effects from these mechanisms cannot be reasonably anticipated. As such, aquatic toxicity presents the most likely potential risk for aquatic organisms.

### MEPC 61/2/9 Annex, page 48

I:\MEPC\61\2-9.doc 

### Tables 2 and 4 present aquatic toxicity data located in literature for a variety of species, endpoints, and exposure periods. It is important to note that the effect concentrations for all DBPs are notably higher than the measured concent rations of DBPs in ballast water discharge. For instance, the overall lowest effect concentration located for all DBP substances is an acute value of 0.028 mg/L (28 μg/L) for MCAA (Table 2). The highest concentration of MCAA measured in ballast water discharge was 1.20 μg/L. As such, although aquatic toxicity presents the most likely potential risk, one can reasonably conclude that the risk is low. Further, as discussed in section 11.4 and below in section 11.13, the whole effluent toxicity data confirms a low potential aquatic toxicity risk.

11.13 Comparison of effect assessment with discharge toxicity

As discussed in section 11.12 above, the e ffects assessment establishes that aquatic toxicity, rather than bioaccumulation or sediment toxicity, presents the most likely potential risk to aquatic organisms. However, the aquatic toxicity data for DBPs, when compared the measured DBP levels in treated/neutralized ballast water discharge, suggests that aquatic toxicity risks are low.

The low potential aquatic toxicity identified in the effects assessment is confirmed when compared to whole effluent toxicity (WET) data for ballast water discharge from the BalPure ®


### system. The concentrations of DBP substances (μg/L range) in treated/neutralized discharge are substantially lower than the aquatic effect concentrations found in literature (mg/L range). Further, with the exception of testing with one species ( Acartia tonsa ), all WET tests after neutralization with bisulfite resulted in E(L)C 50 

### and/or NOEC values ≥ 100% ballast water sample.

The acute aquatic toxicity data for ballast water discharge presented in Table 3 suggest no apparent ecotoxicity for all end points in five of six species tested (E(L)C 50 

### and/or NOEC
values of ≥ 100% ballast water sample). For one species, Acartia tonsa , an effect was observed in one of four acute tests with a low salinity sample (Day 1). In this sample, a moderate effect was observed in the two highest test concentrations (100% and 32% sample), resulting in a NOEC of 18% volume (Grontmij|AquaSense, 2009). This acute test is considered an anomalous data point for several reasons. First, a total of eight ecotoxicity tests (4 acute and 4 chronic) were performed with Acartia ; only one acute test resulted in a moderate effect. Second, during tests with Acartia moderate effects were also noted in a control (untreated, NIOZ harbour water) sample (EC 20 

### of 58% sample) (Grontmij|AquaSense, 2009). A possible explanation for the moderate toxic effect in the treated and control samples is the presence of Phaeocystis, an algal species known to be abundant in the NIOZ harbour and which excretes allelochemicals. Although not a highly toxic algal species, the massive blooms often result in ecosystem effects (Veldhuis and Kools, 2009). Phaeocystis was present in the NIOZ harbour during the whole season of testing but was particularly abundant during the first low salinity test cycles (Veldhuis and Kools, 2009), which corresponds with
when effects were observed in the Acartia tests.

In addition to the above points, it should be noted that STDN performed aquatic toxicity testing with six taxonomic groups, rather than just the three required groups (algae, crustacean, and fish). Both acute and chronic (sub-lethal) tests were performed. Further, discharge toxicity was evaluated for two different salinities (high and low salinity) and at two different time periods after treatment/neutralization (1 and 5 days). Treated/neutralized ballast water discharge tests with all of the five other taxonomic groups under these variable conditions were unaffected at 100% sample. These facts allow for increased confidence in
the conclusion that the 18% NOEC result for Acartia is an anomaly data point among 8 tests with this species and the only one of six ta xonomic groups having a moderate effect. No toxic effects were observed in all other acute (Table 3) or chronic (Table 5) tests.

### MEPC 61/2/9 Annex, page 49

I:\MEPC\61\2-9.doc 

### Lastly, previous chronic ecotoxicity studies ca rried out for Basic Approval at the treatment concentration of 15.0 mg/L HOCl resulted in no ecotoxicity (NOEC = 100% sample) in any of the four species tested (MEPC 60/2/9, Table 5).

Considering all of the above information, although aquatic toxicity is identified as the most likely potential for risk to aquatic organisms, discharge toxicity testing results suggest the potential risk is extremely low.

12 RISK ASSESSMENT

The potential risks presented by having the BalPure ® 

### Ballast Water Management System (BWMS) on board are discussed in section 12. 1 and the potential risks to human health are presented in section 12.2. Section 12.3 addresses risks to the aquatic environment.

12.1 Risk to safety of ship

Additional information regarding corrosion to that presented in the dossier for Basic Approval submitted in August 2009 (MEPC 60/2/9) is presented in this section to address recommendations and comments by the G ESAMP-BWWG (MEPC 60/2/16, annex 7). The additional data presented in this Final Approv al dossier for sodium hypochlorite (or TRO
as Cl 2 

### ) produced by the BalPure ® 

### system indicate that there is a low potential for corrosion of

the ballast water tanks.

12.1.1 Corrosion

The following information and evaluations making use of the GESAMP-BWWG recommendations support that there is a low potential for corrosion of ballast water tanks due to the effect of sodium hypochlorite (or TRO as Cl 2 

### ).

An extensive search was conducted for published literature on the topic of sodium hypochlorite's
effect on corrosion in seawater. A review of these studies was conducted and the results are discussed in the paper, " Effect of hypochlorite on the corrosion of carbon steel in ballast water

tanks " by Dr. Kenneth Hardee, Ph.D. and Prof. Giuseppe Faita, Ph.D. (appendix A.7, Hardee and Faita, 2010). The authors generally confer that the corrosion risk would not be significantly in excess of that for seawater alone in an existing corroded ballast water tank. Dr. Hardee explains that by extrapolating data from Song, et al. (2009) for 5 mg/L chlorine, the corrosion rate in the non-closed (flowing) system would be 0.104 mm/yr or only a 17% increase from that of seawater alone. The corrosion rate will be much lower where there is existing rusted steel and/or the system is closed (semi-stagnant) and has a specific chlorine demand similar to applications with the STDN BalPure ® 

### BWMS. Kim, et al. (2009) further supports the calculations that a ballast tank with 5 mg/L chlorine will have no more than a small effect on the corrosion rate (appendix A.7, Hardee and Faita, 2010). Also the literature indicates that the corrosion rate will slow as there is a buildup of surface rust on the steel, which restricts diffusion of the hypochlorite to the metal surface, although the effect is very difficult to quantify.

In addition, the Hardee and Faita paper (appendix A.7) draws on corrosion and hypochlorite chemistry, findings from the relevant published literature, and directly applies this to operating
data from land-based tests of the STDN BalPure ® 

### BWMS conducted at the Royal Netherlands Institute for Sea Research (NIOZ), Texel, The Netherlands, and Maritime Environmental Resource Centre (MERC), University of Maryland. The Hardee and Faita paper (appendix A.7) presents and compares the corrosion rate of a carbon steel ballast water tank exposed to hypochlorite as a closed system to the typical value for carbon steel structures fully immersed in free flowing seawater. The paper indicates that the corrosion risk is not significantly in excess of that for seawater alone. To further support the opinions regarding corrosion, STDN has submitted the Hardee and Faita paper to BUREAU VERITAS, seeking third party verification.

### MEPC 61/2/9 Annex, page 50

I:\MEPC\61\2-9.doc 

### Ballast tank and pipe coating suppliers have conducted independent tests relating to the impact of seawater and treated seawater on t heir coatings. Ameron, as one of these coatings vendors, sees no effect with 5 mg/L chlorine in seawater on their coating as stated in a letter to STDN (appendix A.7).

Per the German Administration's request, STDN has included Table 1 in appendix A.7, which outlines point-by-point the recommendations for corrosion testing contained in document MEPC 59/2/16 in column one and a response to what extent these guidelines were met in the second column by the BMT (2004) study presented in the Basic Approval dossier.

We acknowledge that the information provi ded therein, though informative and germane to corrosion of steel and coated steel in ballast water applications with chlorine, do not fully meet the recommendations outlined in document MEPC 59/2/16. In consequence, and in support of the conclusions of the paper by Dr. Kenneth Hardee and Prof. Giuseppe Faita that corrosion risk is not significantly in excess of that for seawater alone, we have voluntarily contracted Corrosion Testing Laboratories (CTL), Inc. to complete six months of corrosion tests to fully meet the guidance contained in document MEPC 59/2/16 as recommended by the Group. The results of the study will be consi dered as part of the Type Approval process
with the German Administration.

12.2 Risks to human health

As discussed in section 1.2, Severn Trent De Nora submitted an application dossier for Basic Approval in August 2009 (MEPC 60/2/9). That dossier was reviewed during the 12th meeting of the GESAMP-BWWG in December 2009 and Basic Approval was recommended. The Group considered the human health risk assessment information "sufficient to allow the Group to recommend Basic Approval" (comment 0. 10) and "that the human exposure assessment submitted by the Applicant makes possible to conclude that the operation of this BWMS poses no unacceptable risk to ships' crew, technicians and to the general public" (comment 4.4.2). However, as noted in the comments listed in section 1.2, a number of recommendations
were made as follows:

.1 The Group recommended to take into consideration the human exposure during sampling of ballast water at discharge (inhalation, dermal contact), as well as during periodic sediment cleaning (inhalation, dermal contact). These scenarios should also be considered in the conceptual exposure model (CEM).

.2 The Group recommended that the data sets on the analysis of Active Substance, Relevant Chemicals and Other Chemicals in treated ballast water should be further investigated during land-based and shipboard testing.

.3 The Group recommended that confirmation by further testing should be performed, that there will be no unacceptable risks (to ship safety, human health, or the environment) due to the chemical composition of the ballast water treated by this BWMS.

The following subsections from the dossier for Basic Approval have been revised to consider additional potentially affected receptor groups (ballast water samplers or persons removing tank sediment). Differences in chemical composition of ballast water discharge based on land-based testing results are compared to the previously reported level of sodium bisulfite and maximum levels of bromate ion, THMs, and HAAs measured during studies of the BalPure ® 

### system conducted by the University of Washington (Sos ik and Herwig, 2009; as reported in Tables 27 to 29 of the application dossier for Basic Approval). Risks to receptors potentially exposed to treated ballast water discharge are re-quantified using the land-based testing results.

### MEPC 61/2/9 Annex, page 51

I:\MEPC\61\2-9.doc Exposure

Assessment

Review &

Assessment of Toxicological

Data

Risk
Quantification Uncertainties

Evaluation Risk Assessment

Conclusions Hazard

Identification (Data Review/

COPC Selection ) 

### The evaluation presented herein supplements the evaluation presented in the application dossier for Basic Approval in two ways: (1) risks for technicians or others who may be exposed during ballast water discharge sampling are evaluated quantitatively, and (2) risks to receptors previously evaluated for potential exposure to treated ballast water discharge have been revised using the land-based testing results to estimate exposure.

12.2.1 Introduction

Quantitative human health risk assessments generally follow the process outlined below:

Step 1 Step 2 Step 4 Step 5 Step 6

Step 3



### With respect to the potential human health risks associated with the BalPure ® 

### BWMS, Step 1 is the hazard identification process. The BalPure ® 

### operational system is reviewed, and chemicals stored on the ship and added to the syst em or produced in situ at concentrations potentially harmful to human health are carried forward in the quantitative risk assessment as the chemicals of potential concern (COPCs). In Step 2 , COPC-specific toxicity values for use in the quantitative risk analysis are compiled via an exhaustive literature search. If no toxicity data exists, information from appropriate surrogat es and/or structurally similar chemicals may be used. For COPCs without toxicity informati on, quantitative risk evaluation is not possible.

In Step 3 , exposure scenarios are developed (1) to describe the potential exposures on board during routine vessel operations including operation, monitoring and maintenance of

the BalPure ® 

### BWMS and (2) to describe the potential exposures on and off board during equipment failure/and or accidental release of the COPCs, and (3) to provide a basis for quantifying those exposures. Each exposure scenario addresses the COPCs, the potential route or mechanism of exposure, and potentially exposed human populations (known as "receptors"). When operation-specific data for scenario development are unavailable, conservative values found in the appropriate regulatory guidance are used.

In Step 4 , the toxicity and exposure assessments are integrated into quantitative expressions of risks. This includes COPC-specific, multi-pat hway risks for each of the potential receptors. The risk values presented in a risk assessmen t are conditional estimates derived from a considerable number of conservative, health-protective assumptions about exposure and toxicity. Thus, to place the risk estimates in proper perspective, it is important to specify the assumptions and uncertainties inherent in the risk assessment. This process is conducted in Step 5 . This step may also involve the reevaluation of data or the identification of additional data requirements to decrease uncertainty. Step 6 involves the development and presentation of conclusions that can be inferred from the findings of the risk assessment. This step provides risk managers with insight into the interpretation of the risk assessment results.

### MEPC 61/2/9 Annex, page 52

I:\MEPC\61\2-9.doc 

### 12.2.2 Hazard identification/chemical of potential concern selection

The chemicals of potential concern (COPCs) associated with the use of BalPure ® 

### BWMS were selected by determining which chemicals, either stored and added to the system or
formed in situ , have the potential to adversely impact human health under either routine operating conditions, maintenance operations, or during an emergency resulting in an unexpected release.

As described in sections 1 and 2, the BalPure ® 

### BWMS is a nearly closed system that produces the disinfection agent, sodium hypochlorite (as a mixture of hypochlorous acid/hypobromous acid), via electrolysis of seawater. Hydrogen gas, a secondary by-product
of the in situ electro-chemical process, is vented to the atmosphere (using blowers) at concentrations of less than 1%. However, exposure to atmospheric gases typically are not included in risk assessment, and the safety features inherent in the BalPure ® 

### BWMS as well as the physical properties of hydrogen gas suggest it is unlikely to accumulate to levels of concern (e.g., above the LEL). Therefore, as i ndicated in section 2.3.3, hydrogen gas is not
considered relevant for the assessment of human health risks. Sodium bisulfite is added to de-chlorinate the ballast water as it is discharged from the ship.

U PDATED TEXT 

### P ERTINENT 

### T O 

### F INAL 

### A PPROVAL 

### A PPLICATION



### In the application dossier for Basic Approval, the final list of COPCs carried forward in the risk assessment included total residual oxidants (TRO) evaluated as hypochlorous acid, total THMs (including chloroform, bromoform, bromodichloromethane, and chlorodibromomethane), total HAAs (including bromochloroacetic acid, mono-, di- and trichloroacetic acids, and mono- and dibromoacetic acids), bromate and sodium bisulfite. With respect to chemicals detected in treated ballast water, this risk assessment for Final Approval is revised to evaluate only chemicals detected during land-based testing.

As described in section 2.3, chemicals included for Basic Approval but not detected in the land-based testing of the BalPure ® 

### system at NIOZ include chloroform, trichloroacetic acid, and bromate ion. Chemicals detected during land-based testing of the BalPure ® 

### system at NIOZ but not previously considered in the risk assessment are the HAAs tribromoacetic acid and dibromochloroacetic acid, and 2,4,6-tribro mophenol (TBP). The re-quantification of risks presented in section 12.2.5 includes tribromoacetic and dibromochloroacetic acids in the total

HAA calculation.

As discussed in section 2.3.2, 2,4,6-TBP was not detected in measurable concentrations in land-based tests using high salinity water (section 11.3, Tables 22 and 23). 2,4,6-Tribromophenol was detected at low levels (maximum = 1.3 μg/L) in ballast water discharged during the low salinity test cycles, but also was detected in the untreated (control) samples at the same, or higher, concentrations. 2,4,6-tribromophenol has been documented to occur in natural environments, either as a pollutant from anthropogenic sources (wood industry, antifungal use) or from natural production by marine benthic organisms (OECD SIDS, 2003). Despite its detection in source (control) water, 2,4,6-TBP is added to the list of
COPCs carried forward in this risk assessment.

Chloroform was not detected in land-based discharge samples, and risks from exposure to
THMs will be evaluated based on the total concentration of all other THMs detected. Bromate ion was not detected during land-based testing, and therefore has not been
considered as a COPC in this revised risk assessment.

### MEPC 61/2/9 Annex, page 53

I:\MEPC\61\2-9.doc 

### 12.2.3 Human Exposure Scenario

The US EPA (1989) defines an exposure pathway as "the course a chemical or pollutant takes from the source to the organism exposed". An exposure route is "the way a chemical or pollutant enters an organism after contact" (US EPA 1989). A complete exposure pathway requires four key elements: chemical sources; migration routes (i.e. environmental transport); potentially exposed human receptors; and routes of exposure to impacted media (e.g., ingestion of chemicals in water). All four factors are required for a complete exposure pathway; if any one factor is missing, the pat hway is considered incomplete. Because an incomplete pathway does not pose a potential health hazard, incomplete exposure pathways are not included in this health risk assessment. Potential human receptor groups and exposure routes are described below.

U PDATED TEXT 

### P ERTINENT 

### T O 

### F INAL 

### A PPROVAL 

### A PPLICATION



### The exposure scenarios evaluated quantitatively in the application dossier for Basic Approval were: (1) STDN BalPure ® 

### BWMS Technicians exposed (via dermal contact and incidental ingestion) to hypochlorous acid during maintenanc e activities and/or sodium bisulfite during chemical resupply, (2) ship's crew/dock work ers exposed (via dermal contact) to COPCs in treated ballast water spray drift, and (3) the general public who may swim in the vicinity of (and incidentally ingests and has dermal contact with) recently discharged ballast water

associated with the BalPure ® 

### system. However, the Group recommended the consideration of exposure during sampling of ballast water at discharge (inhalation, dermal contact), as well as during periodic sediment cleaning (inhalation, dermal contact), which has been added

to the discussion below.

12.2.3.1 Potential exposure pathways

The conceptual exposure model (CEM) provides the basis for a comprehensive evaluation of the risks to human health by identifyi ng the mechanisms through which people may be exposed to COPCs. The CEM traces the COPCs in a logical migration from their sources through various release mechanisms and exposure routes to potentially affected receptor groups. The CEM identifies the exposure routes that are potentially complete under the given use(s). These pathways are evaluated in the quantitative risk assessment for each receptor. The CEM also facilitates the analysis and screening of exposure pathways not likely to pose significant risks.

Primary, secondary, and tertiary sources of COPCs associated with the BalPure ® 

### BWMS are listed in the CEM (Figure 3). The primary sources of COPCs include the in situ production of sodium hypochlorite, the sodium bisulfite storage tanks and associated pipelines, and the
treated ballast water itself. Chemicals associated with the BalPure ® 

### BWMS are expected to remain contained, unless a storage or pipeline failure occurs. Such a release would allow COPCs to migrate to secondary and tertiary sources. For example, accidental spills and pipe or tank failure could result in the release of COPCs onboard the vessel or to seawater. From these secondary sources, the COPCs ma y migrate to tertiary sources such as volatizing into air within enclosed spaces on the vessel or in outdoor air, or migration to shorelines and/or docking areas.

As shown in Figure 3, only exposure to COPCs resulting from leaks of storage tanks, pipelines and ballast tank discharges are evaluated quantitatively in this risk assessment. This is because no exposure is anticipated during normal operating conditions, because
chemicals used in the BalPure ® 

### BWMS are contained within a closed system (hypochlorous acid is produced in situ and is injected directly into the ballast system; sodium bisulfite is injected into the ballast water as it is discharged from the ship), While both the chemical

### MEPC 61/2/9 Annex, page 54

I:\MEPC\61\2-9.doc 

### storage tanks and ballast tanks are vented, vent lines are directed to the atmosphere or to spaces within the ship with proper ventilation. Significant volatilization of COPCs from solution (from either storage tanks or treated ballast water) into indoor or outdoor air is extremely unlikely, and is not evaluated quantitatively. It is noted, however, that the trihalomethanes produced as disinfectant by-products are volatile and hydrophobic, and as such, could be inhaled near ballast water or vent air outlets. While this inhalation pathway is not evaluated in the quantitative risk asse ssment, potential exposures and risks associated with vent air during ballasting and deballasting were discussed in section 12.2.5.5 of the application dossier for Basic Approval, and have been revised herein (now section 12.2.5.6) to reflect maximum concentrations of THMs detected during land-based testing.

U PDATED TEXT 

### P ERTINENT 

### T O 

### F INAL 

### A PPROVAL 

### A PPLICATION



### As noted by the Group, exposure to treated ballast water also could occur during discharge sampling. In addition, workers could be exposed to treated ballast water when cleaning sediment from the tanks, although this activity would be conducted following established and standard confined space safe entry practices, and persons engaged in this activity would be wearing personal protective equipment (PPE). These additional potential exposure scenarios are considered in the risk assessment, as discussed below.

12.2.3.2 Identification of potentially exposed populations

The BalPure ® 

### system is designed to operate automatica lly, with the system processes during ballasting and deballasting started and stopped based on electronic signals. Therefore, under normal operating conditions, neither STDN BalPure ® 

### technicians nor the ship's crew is expected to have contact with the BWMS-related COPCs. Because the BalPure ® 

### BWMS is closed system, exposure to the Active Subst ance, disinfection by-products, or sodium bisulfite is highly unlikely.

As shown in Figure 3, people with the greatest potential for exposure to BalPure ®



### BWMS-related COPCs are STDN BalPure ® 

### technicians involved in routine maintenance and repair, or chemical resupply activities. Thes e technicians, or others, could be exposed to COPCs in treated ballast water during routine discharge sampling. Although unlikely, ship's crew on board and in the spaces where the system components are present could also be exposed to COPCs during a pipeline or chemical tank failure; it is anticipated that these potential exposures would be less than those for STDN technicians conducting routine maintenance or chemical resupply. Because ballast water tanks remain closed at all times (with the exception of planned inspections/repairs of empty tanks) STDN technicians and the ship's crew are not expected to have direct contact with treated ballast water, although this potential exposure pathway is evaluated below. Further, either the ship's crew or dock workers could have dermal contact with released ballast water as a result of spray drift. As shown in Figure 3, while STDN technicians, ship's crew, or dock workers potentially could inhale chemicals volatilizing from treated ballast water, these source-exposure pathways are considered highly unlikely and are not evaluated quantitatively.

Others with potential for COPC contact include the general public recreating at beaches near areas where treated ballast water has been discharged from the ship, although this exposure scenario is highly unlikely. These receptors and the potential exposure pathways are

summarized below.

### MEPC 61/2/9 Annex, page 55

I:\MEPC\61\2-9.doc SOURCES

Primary Secondary Tertiary

Vessel Surface

Seawater

Dock/Shoreline



### • Pathway is or might be complete; sufficient data available for quantitative evaluation

X Pathway is or might be complete, but judged to be minor; not evaluated quantitatively

1 STDN Technician exposure considered worst-case scenario for anyone working onboard vessel.

2 Not evaluated quantiatively in risk assessment; semi-qualitatively evaluation provided.

Pathway is not complete; no evaluation required STDN

Technician/Other

- Discharge Sampling

X



### • Ship's Crew -

Accidental

Release

X 1

X

X 2



### • On Board

X Dermal Contact/ Incidental Ingestion

Inhalation

X Exposure Routes



### •

X Ship's Crew -

Ballast Tank

Entry

X Release from

Ballast Tanks

Dermal Contact/ Incidental Ingestion X Inhalation X General

Public Off Board

Dock

Workers



### • X Spills/Leaks from Storage Tanks, Pipelines or BWTS Vapors/Indoor Air

Vapors/Outdoor Air



### • STDN

Technician -

Maintenance



### Figure 3: Conceptual Exposure Model, BalPure ® 

### System

.1 STDN BalPure ® 

### BWMS Technicians: STDN technicians or properly

trained BalPure ® 

### personnel are the only receptors who would work directly with the BWMS, including routine maintenance and chemical resupply of sodium bisulfite, and therefore have the greatest potential for actual exposure. Although proper chemical st orage and handling, safety training, and use of appropriate PPE would prevent direct contact with COPCs, technicians could be exposed to hypochlorous acid, sodium bisulfite, or treated ballast water during maintenance activities via:

- incidental ingestion of COPCs during routine maintenance and chemical resupply activities;

- dermal contact with COPCs during routine maintenance and chemical resupply activities; and

- inhalation of COPC vapors or mists in air during routine maintenance and chemical resupply activities.

The potentially complete and quantifiable exposure pathways for STDN

BalPure ® 

### technicians include: a) incidental ingestion of and dermal contact with hypochlorous acid at maximum concentrations of 1,000 mg/L, and b) incidental ingestion of and dermal contact with sodium bisulfite during chemical resupply at maximum concentrations of 380,000 mg/L.

For hypochlorous acid, potential exposure is further mitigated by a pipeline flushing cycle that is engineered into the system. For instance, after generation of the Active Substances and the ballasting operation is complete, a 10 minute cycle is initiated by the PLC to the electrolyzer cells and injection pipelines with seawater. The same can be done for the sodium bisulfite delivery piping when a deballasting operation is complete, if needed to enhance the safety of an installation. These flush cycles ensure that pipelines do not remain filled with chemicals when the BWMS is not in operation.

### MEPC 61/2/9 Annex, page 56

I:\MEPC\61\2-9.doc 

### .2 STDN BalPure ® 

### BWMS Technicians (or others) engaged in sampling of

treated ballast water: BalPure ® 

### technicians and/or ship's crew will likely be responsible for sampling treated/neutralized ballast water at the point of discharge. Although use of appropriate PPE would prevent direct contact with COPCs, technicians could be exposed to COPCs in treated ballast water during sampling via:

- dermal contact with COPCs during discharge sampling; and

- inhalation of COPC vapours or mists in air during discharge sampling.

However, as discussed previously, during deballasting operations, residual chlorine present in the ballast tank is neutralized (de-chlorinated) with sodium bisulfite just prior to disc harge from the ship. The trihalomethanes are the only disinfectant by-products identified as volatile (see Table 17 of this dossier and 18 in the dossier for Procedure (G9) Basic Approval), and therefore could be inhaled near the ballast water discharge outlet. However, it is anticipated that concentrations in air would be low and immediately mixed into the surrounding atmosphere. Therefore, the only potentially complete and quantifiable exposure pathway for ballast water samplers is dermal contact with COPCs in discharged ballast water, including hypochlorous acid, THMs, HAAs, 2,4,6-tribromophenol, and sodium bisulfite at the maximum residual ballast water concentrations detected during land-based testing: <20, 0.845, 0.375, 0.0013, and 8.0 mg/L, respectively (see section 11.3 of Basic Approval dossier and section 11.3 herein). It is also important to note that treated ballast water discharge will be neutralized with sodium bisulfite, so the maximum residual ballast water concentration for hypochlorous acid is overly conservative because it does not consider neutralization. This exposure scenario is similar to the ship's crew/dock worker scenario included in the Basic Approval dossier (and described below), but would not be accidental and is evaluated with possible greater frequency.

.3 Ship's crew: Under normal operating conditions, the ship's crew has limited

to no interaction with the BalPure ® 

### BWMS. The system and piping are located in areas where the crew may be present, but normal ballasting and deballasting modes of the BalPure ® 

### system are controlled automatically and do not require chemical contact. However, this group has the potential to be exposed to sodium bisulfite wh ile chemical-resupply activities take place, or if a pipeline or storage tank fails, or to any COPCs during a failure of the BalPure ®


### system. Exposure to treated ballast water is highly unlikely, since the tanks are opened for required inspections only when empty, although the potential for exposure to ballast water spray drift exists. The actual exposure potential for this group is extremely low, but the possible exposure routes include:

- incidental ingestion of the COPCs during an accidental release;

- dermal contact with COPCs during an accidental release; and

- inhalation of COPC vapors or mists in air during an accidental

release.

As previously indicated, accidental release of hypochlorous acid and/or sodium bisulfite is expected to result in exposures smaller than those for

### MEPC 61/2/9 Annex, page 57

I:\MEPC\61\2-9.doc 

### STDN BalPure ® 

### technicians engaged in routine maintenance and chemical resupply. Moreover, as described in section 8.1.3.2 of the application dossier for Basic Approval, STDN technicians and ship's crew will be trained to respond to sodium bisulfite spills; therefore these exposure scenarios are not included in the quantitative risk assessment. The only potentially complete and quantifiable exposure pathway for ship's crew is dermal contact with COPCs in discharged ballast water, including hypochlorous acid, THMs, HAAs, 2,4,6-tribromophenol, and sodium bisulfite at the maximum residual ballast water concentrations, as described above.

.4 Ship's crew (or others) responsible for ballast tank sediment cleaning: Workers engaged in tank cleaning could be exposed to residual treated ballast water remaining in the tanks (via dermal contact or incidental ingestion, or to any vapours that remain in the tank once it has been opened). However, because standard confined space entry protocols that are required by applicable regulations will be implemented prior to tank entry, this route of exposure is not considered complete. For instance, protocols such as, but not limited to, those outlined by the International Association of Classification Societies Ltd. (IACS) Confined Space Safe Practice (2007) are performed as standard operating procedure prior to ballast tank entry. For the purposes of example, these practices may include:

- a safety meeting should be held prior to tank entry/survey;

- Entry Permit should be obtained for the space to be entered;

- identify the hazards and assess the risks;

- evaluate ventilation of the space;

- ensure that a standby and/or rescue team is in place;

- check and evaluate gas measurements taken

− as a minimum, oxygen measurements should be carried out before entry into the enclosed space;

- use of personal gas measuring equipment during the entry/survey; and

- evaluate if special clothing and/or equipment are required.

Given the standard practices and mitigation measures implemented prior to any ballast tank entry, the possibility of exposure to ballast water related chemicals is very low. Therefore, as illustrated in the revised conceptual exposure model shown in Figure 3, only the ballast water sampling scenario has been added for quantitative evaluation in this risk assessment.

.5 Dock workers: Under normal operating conditions, dock workers will have

no interaction with the BalPure ® 

### BWMS or chemical resupply activities. While exposure to treated ballast water is highly unlikely, the potential for exposure to ballast water spray drift exists. The actual exposure potential for this group is extremely low, but the possible exposure routes include:

- dermal contact with COPCs in ballast water spray drift.

### MEPC 61/2/9 Annex, page 58

I:\MEPC\61\2-9.doc 

### The only potentially complete and quantifiable exposure pathway for dock workers is dermal contact with COPCs in discharged ballast water, including hypochlorous acid, THMs, HAAs, 2,4,6-tribromophenol, and
sodium bisulfite at the maximum residual ballast water concentrations. This quantitative evaluation is identical to that for ship's crew.

.6 General public: Although it is unlikely that the general public would recreate near docked ships, it is possible that recreation areas could be located downstream of shipping docks. While any COPC releases from the ship would be immediately diluted into surrounding seawater, the general public (adults or children) could be exposed to COPCs via:

- incidental ingestion of ballast water COPCs discharged to seawater near the shoreline;

- dermal contact with ballast water COPCs discharged to seawater near the shoreline; and

- inhalation of ballast water COPC vapors or mists in outdoor air

near the shoreline.

The potentially complete and quantifiabl e exposure pathways for swimmers include: incidental ingestion of and dermal contact with hypochlorous acid, THMs, HAAs, 2,4,6-tribromophenol, and sodium bisulfite in recently discharged ballast water. It is conservatively assumed that maximum residual ballast water COPC concentrations are diluted 100-fold prior to contact with beachgoers.

In the application dossier for Basic A pproval, the chemical composition of
treated ballast water was based on maximum levels of THMs and HAAs measured during the studies of the BalPure ® 

### system conducted by the University of Washington (Sosik and Herwig, 2009; as reported in Tables 27 to 29 of the Basic Approval dossier). Since that time, land-based testing has been conducted, with the maximum concentrations shown in Tables 22 and 23. In regards to hypochlorous acid, the maximum treatment dose (20 mg/L TRO as Cl 2 

### ) presented in STDN's application dossier for Basic Approval was also used in this hu man risk assessment to maintain a high level of conservatism. However, the maximum treatment dose applied during land-based testing was 15 mg/L TRO as Cl 2 

### . Because the human risk assessment is performed using a 20 mg/L dose any risks due to exposure of hypochlorous acid can be considered less than presented here. Table 30 provides a summary of the exposure point concentrations (EPCs) discussed above and used this risk assessment, and compares them to the values used in the dossier for Basic Approval. Overall, there is very little difference in the maximum concentrations of THMs and HAAs

between the two tests.

### MEPC 61/2/9 Annex, page 59

I:\MEPC\61\2-9.doc 

### Table 30: Comparison of Basic Approval and Land-based Ballast Water Residual COPC Exposure Point Concentrations

Basic and Final Approval
Dossiers STDN

Technicians:

Maximum
Concentration in System Basic Approval
Dossier

Maximum
Residual Ballast

Water
Concentrations Land-based
Maximum

Residual Ballast
Water
Concentrations Land-based Diluted (100X)

Residual Ballast
Water
Concentrations

COPC mg/L mg/L mg/L mg/L
Hypochlorous Acid 1.00E+03 2. 00E+01* 2.00E+01* 2.00E-01*

Bromate NA 4.20E-02 No t detected Not detected

THMs NA 1.10E+00 8.45E-01 8.45E-03

HAAs NA 2.42E-01 3.75E-01 3.75E-03
2,4,6-Tribromophenol NA NA 1.30E-03 1.30E-05

Sodium bisulfite 3.80E+05 2.00E+00 8.00E+00 8.00E-02

NA = Not applicable * = Assumed as worst case residual; maximum treatment dose concentration



### 12.2.3.3 Quantitative exposure assessment

As described above, although highly unlikely, STDN BalPure ® 

### technicians could have direct contact (ingestion and dermal contact) with COPCs within the BWMS during maintenance activities and to sodium bisulfite during chemical resupply activities. STDN BalPure ®


### technicians or others could have dermal expos ure to treated ballast water during discharge sampling and ship's crew or dock workers could have dermal exposure to ballast water spray drift. Beachgoers may recreate in the vicinity of ballast water discharges. Intake factors are used to determine the amount of COPC that each receptor is potentially exposed to via each exposure route, and are used to evaluate both cancer risk and non-cancer hazard.

The following equation was used to quantify intake from the dermal contact pathway:

I
w



### = (C

w 

### )(SA)(PC)(CF)(ET)(EF)(ED) / (BW)(AT)

Where:

I
w 

### = intake from dermal contact with COPC in ballast water/solution (mg/kg-d) Cw = maximum concentration of a COPC in ballast water/solution (mg/L) SA = skin surface area in contact with ballast water/solution (cm 2 

### /d) PC = dermal permeability coefficient (cm/hr), chemical-specific CF = conversion factor 10-3 (L/cm 3 

### ) ET = exposure time (h/d) EF = event frequency (d/y) ED = exposure duration (y) BW = body weight (kg) AT = averaging time (d), ED x 365d/y (non-carcinogens), 70y x 365d/y (carcinogens)

### MEPC 61/2/9 Annex, page 60

I:\MEPC\61\2-9.doc 

### The following equation was used to quantify intake from the incidental ingestion pathway:

I
w



### = (C

w 

### )(IngR)(EF)(ED) / (BW)(AT)

Where:

I
w 

### = intake from incidental ingestion of COPC in ballast water/solution (mg/kg-d)
C

w 

### = maximum concentration of COPC in ballast water/solution (mg/L) IngR = ingestion rate (L/day) EF = event frequency (d/y) ED = exposure duration (y) BW = body weight (kg) AT = averaging time (d) - ED x 365d/y (non-carcinogens), 70y x 365d/y (carcinogens)

The receptor-specific exposure parameters used to estimate COPC intake based on the equations above are summarized below and the resulting intake factors summarized in Tables 31 and 32. As shown in Tables 31 and 32, the intake equations described above for the general public (beachgoers) are age-adjusted to account for six years of exposure as a child and 24 years of exposure as an adult. This approach is consistent with guidance (US EPA 1989 and 1991e), and accounts for any differences in exposure assumptions

between children and adults.

.1 STDN Technicians

The adult exposure factors used to quantify potential exposure to hypochlorous acid during maintenance of the BalPure ® 

### BWMS or to sodium bisulfite during chemical resupply are:

- Ingestion Rate: While incidental ingestion is likely to be only a fraction of the ingestion rate for swimming, 0.05 L/hour is conservative and therefore used (US EPA 1989).

- Skin Surface Area Available for Contact: During an accidental spill, technicians or workers may have significant contact with hands and arms, which results in a skin surface area of 3,300 cm 2 

### (US EPA 2004).

- Permeability Constant: Chemical-specific; for inorganics without a permeability coefficient, and especially for ionized chemicals, guidance recommends using 0.001 cm/hour (US EPA 2004).

- Body Weight: The adult body weight typically applied in risk assessment is 70 kg (US EPA 2002).

- Exposure Time: The exposure time is assumed to be 0.25 hours per event, is based on best professional judgment.

- Event Frequency: Based on best professional judgment, an exposure frequency of 1 spill event per year is used.

- Exposure Duration: Based best professional judgment, the exposure duration is 10 years.

### MEPC 61/2/9 Annex, page 61

I:\MEPC\61\2-9.doc 

### - Averaging Time: The life expectancy of 70 years (25,550 days) was used as the averaging time for exposure to carcinogenic contaminants (US EPA 2002). The averaging time for non-carcinogenic effects is equal to the exposure duration of 10 years (3,650 days).

.2 STDN BalPure ® 

### BWMS Technicians (or others) responsible for ballast water discharge sampling

The adult exposure factors used to quantify potential exposure to discharged ballast water during sampling are expected to be similar to those used to quantify ship's crew/dock worker exposure to spray drift, with the exception of a higher event frequency:

- Skin Surface Area Available for Contact: During sampling of ballast water at discharge, crew or workers may have limited contact with hands, arms, and face, which results in a skin surface area of 1,800 cm 2 

### which is based on best professional judgment (10% of total body; US EPA 2004).

- Permeability Constant : Chemical-specific; for inorganics without a permeability coefficient, and especially for ionized chemicals, guidance recommends using 0.001 cm/hour (US EPA, 2004). The value for chloroform, 0.0068 cm/hour, is used as a surrogate for THMs, HAAs, and 2,4,6-tribromophenol (US EPA 2004).

- Body Weight: The adult body weight typically applied in risk assessment is 70 kg (US EPA, 2002).

- Exposure Time: The exposure time is assumed to be 0.25 hours per event, is based on best professional judgment.

- Event Frequency: Based on best professional judgment, an exposure frequency of 52 ballast water discharge sampling events per year is used.

- Exposure Duration: Based on best professional judgment, the exposure duration is 10 years.

- Averaging Time: The life expectancy of 70 years (25,550 days) was used as the averaging time for exposure to carcinogenic contaminants (US EPA, 2002). The averaging time for non-carcinogenic effects is equal to the exposure duration of 10 years (3,650 days).

.3 Ship's Crew/Dock Workers

The adult exposure factors used to quantify potential exposure to discharged ballast water spray drift are:

- Skin Surface Area Available for Contact: During a spray drift incident, crew or workers may have limited contact with hands, arms, and face, which results in a skin surface area of 1,800 cm 2 

### which is based on best professional judgment (10% of total body; US EPA 2004).

### MEPC 61/2/9 Annex, page 62

I:\MEPC\61\2-9.doc 

### - Permeability Constant: Chemical-specific; for inorganics without a permeability coefficient, and especially for ionized chemicals, guidance recommends using 0.001 cm/hour (US EPA 2004). The value for chloroform, 0.0068 cm/hour, is used as a surrogate for THMs, HAAs, and 2,4,6-tribromophenol (US EPA 2004).

- Body Weight: The adult body weight typically applied in risk assessment is 70 kg (US EPA 2002).

- Exposure Time: The exposure time is assumed to be 0.25 hours per event, is based on best professional judgment.

- Event Frequency: Based on best professional judgment, an exposure frequency of 1 spray drift event per year is used.

- Exposure Duration : Based on best professional judgment, the exposure duration is 10 years.

- Averaging Time: The life expectancy of 70 years (25,550 days) was used as the averaging time for exposure to carcinogenic contaminants (US EPA 2002). The averaging time for non-carcinogenic effects is equal to the exposure duration of 10 years (3,650 days).

.4 General Public (Beachgoers)

The exposure factors used to quantify potential exposure to COPCs in discharged ballast water to swimming beachgoers (adults and children) are described below. As discussed above and shown in Tables 31 and 32, the intake factors used to evaluate cancer risk for beachgoers are age-adjusted to account for differences in exposure assumptions between children and

adults.

- Ingestion Rate: The ingestion rate for swimming, 0.05 L/hour, is used (US EPA 1989).

- Skin Surface Area Available for Contact: The average of the 50th percentile total skin surface area for adults is 18,000 cm 2 

### and for children is 6,600 cm 2 

### (US EPA 2004).

- Permeability Constant: Chemical-specific; for inorganics without a permeability coefficient, and especially for ionized chemicals, guidance recommends using 0.001 cm/hour (US EPA 2004). The value for chloroform, 0.0068 cm/hour, is used as a surrogate for THMs, HAAs, and 2,4,6-tribromophenol (US EPA 2004).

- Body Weight: The adul t and child bo dy weights typically applied in risk assessment are 70 and 15 kg, respectively (US EPA 2002).

- Exposure Time: The US EPA's recommended swimming duration of 60 minutes per event, based on the 50th percentile value (US EPA 1997).

### MEPC 61/2/9 Annex, page 63

I:\MEPC\61\2-9.doc 

### - Event Frequency: Based on best professional judgment, an upper-end exposure frequency of 10 events per year is used.

- Exposure Duration: Based on US EPA guidance, the exposure duration is 30 years, which includes six years as a child and 24 years as an adult (US EPA 2002).

- Averaging Time: The life expectancy of 70 years (25,550 days) was used as the averaging time for exposure to carcinogenic contaminants (US EPA 2002). The averaging time for non-carcinogenic effects is equal to the exposure duration; 24 years as an adult (8,760 days) and 6 years as a child (2,190 days).

Table 31: Summary of Dermal Intake Factors

IF dermal =

IF dermal/adj =

IF dermal = Dermal Intake Factor, L water/kg body weight-day

SA = Surface Area, cm 2

PC = Dermal Permeability Constant, cm/ hour
CF = Volumetric Conversion Factor, 1 Liter/1000 cm 3

ET = Exposure Time, hours/day EF = Exposure Frequency, days/year ED = Exposure Duration, years BW = Body Weight, kg AT = Averaging Time, days

Child Adult (0-6 years)

SA 3300 1800 1800 18000 6600

CF 0.001 0.001 0.001 0.001 0.001

ET 0.25 0.25 0.25 1 1

EF 1 52 1 10 10

ED 10 10 10 24 6

BW 70 70 70 70 15

AT carcino g ens 25550 25550 25550 25550 25550

AT nonarcinogens 3650 3650 3650 8760 2190

PATHWAY-SPECIFIC INTAKE FACTORS:

Carcinogens x PC 4.61E-06 1.31E-04 2.52E-06 3.45E-03 NA
Noncarcinogens x PC 3.23E-05 9.16E-04 1.76E-05 7.05E-03 1.21E-02 Exposure Variable General Public

STDN

Technician Ship's Crew/

Dock Worker STDN

Technician/Other - Sampling

Chemical-Specific Intake Factors via Dermal Contact (IF dermal ), L water/kg body weight-day SA x PC x CF x ET x EF x ED
BW x AT

SA child x PC x CF x ET child x EF child x ED child BW child x AT + SA adult x PC x CF x ET adult x EF adult x ED adult BW adult x AT

NA = Not applicable.

### MEPC 61/2/9 Annex, page 64

I:\MEPC\61\2-9.doc 

### Table 32: Summary of Oral Intake Factors

IF oral =

IF oral/adj =

IF oral = Oral Intake Factor, L water/kg body weight-day
IR = Ingestion Rate, L/hour ET = Exposure Time, hours/day EF = Exposure Frequency, days/year ED = Exposure Duration, years BW = Body Weight, kg AT = Averaging Time, days

Child
Adult (0-6 years)

IngR 0.05 NA NA 0.05 0.05

ET 0.25 NA NA 1 1

EF 1 NA NA 10 10

ED 10 NA NA 24 6

BW 70 NA NA 70 15

AT carcino g ens 25550 NA NA 25550 25550

AT nonarcinogens 3650 NA NA 8760 2190

PATHWAY-SPECIFIC INTAKE FACTORS:
Chemical-Specific Intake Factors via Oral Ingestion (IF oral ), L water/kg body weight-day

Carcinogens 6.99E-08 NA NA 1.45E-05 NA
Noncarcinogens 4.89E-07 NA NA 1.96E-05 9.13E-05 Exposure

Variable General Public

STDN

Technician Ship's Crew/

Dock Worker STDN

Technician/Other - Sampling IngR x ET x EF x ED
BW x AT

IngR child x ET child x EF child x ED child BW child x AT + IngR adult x ET adult x EF adult x ED adult BW adult x AT

NA = Not applicable



### 12.2.4 Health effects in humans

The objective of this section is to provide information regarding the potential for health risks from exposure to chemicals potentially present in treated ballast water. Specifically, this section describes how dose-response, or toxicity values, are established and used for non-carcinogenic and carcinogenic COPCs. Because only the ingestion and dermal exposure routes are evaluated quantitatively, this section focuses exclusively on oral toxicity values (which are commonly used as surrogates for evaluation of dermal exposure).

12.2.4.1 Acute health effects

With the exception of 2,4,6-tribromophenol, all of the COPCs identified can be skin and eye irritants as described in Table 9 of this dossier and the Basic Approval dossier. Unlike the COPCs previously evaluated, 2,4,6-tribromophenol can be an eye irritant but it has not been demonstrated to irritate the skin (see Table 9).

### MEPC 61/2/9 Annex, page 65

I:\MEPC\61\2-9.doc 

### With the exception of sodium bisulfite, all of the COPCs identified are generated in situ at aqueous concentrations in the μg/L to mg/L range. These in situ generated COPCs are at concentrations too low to cause serious eye and skin irritation. There may be some limited potential for minor eye irritation if there is direct contact with ballast water, due to a combination of the COPCs, salts, and other compounds which may be in the ballast/seawater prior to treatment. Skin irri tation is considered unlikely given the very low concentrations of the COPCs. THMs are known to cause both skin and eye irritation when present at much high concentrations than those present in situ in ballast water (IPCS 2004).

The one COPC which could represent an acute eye and skin hazard is the sodium bisulfite solution stored on the vessel. The MSDS (Table 9 of the dossier for Basic Approval) clearly states that contact with the 38% solution can cause eye and skin irritation. Appropriate PPE should be used when working with this solution to minimize the potential for these acute health effects, and only trained personnel should be handling the concentrated solution (Mallinckrodt, 2006a).

The potential for acute irritation of the nose and throat upon inhalation is unlikely. The THMs which are the most likely COPCs to volatize were considered in a separate inhalation assessment in the dossier for Basic Approval (Table 39). The safe levels used in that inhalation assessment, and updated here (section 12.2.5.6) are considered protective of
irritation of mucous membranes c aused by volatile THMs (OSHA 2009).

The more critical endpoint for potential exposure to ballast water COPCs at low

concentrations are chronic health issues such as liver disease and cancer. These chronic effects are fully addressed in the risk assessment.

12.2.4.2 Non-carcinogenic adverse health effects

For the non-carcinogenic effects of specific constituents, most regulatory agencies assume a dose exists below which no adverse health effects will be seen (US EPA 1989). Below this "threshold" it is believed that exposure to a chemical can be tolerated without adverse effects. Adverse effects manifest only when physiologic protective mechanisms are overcome by exposure to doses above the threshold. The reference dose (RfD), expressed in units of milligrams per kilogram-day (mg/kg-d ), represents the daily intake of a constituent (averaged over a year) per kilogram of body weight that is below the effect threshold for the constituent. It is assumed that non-carcinogenic exposure doses are not cumulative from age group to age group over a lifetime of exposure (US EPA 1989). An RfD is specific to the constituent, route of exposure, and duration over which the exposure occurs.

Agencies, most notably the US EPA, review all relevant human and animal studies for each constituent and select the studies pertinent to the derivation of specific RfDs. Each study is evaluated to determine the no-observable-adverse-effect level (NOAEL) or, if data are inadequate for such a determination, the lowest-observable-adverse-effect level (LOAEL). The NOAEL corresponds to the dose (mg/kg-d ) that can be administered over a lifetime without inducing observable adverse effects. The LOAEL corresponds to the lowest daily dose (mg/kg-d) that can be administered over a lifetime that induces an observable adverse effect. The toxic effect characterized by the LOAEL is referred to as the "critical effect" (US EPA 1989).

To derive an RfD, the NOAEL (or LOAEL) is di vided by uncertainty factors (alternatively known as safety factors) to ensure protection of human health. Uncertainty factors are applied to account for: (1) extrapolation of data from laboratory animals to humans (interspecies extrapolation), (2) variation in human sensitivity to the toxic effects of a constituent (intraspecies differences), (3) derivation of a chronic RfD based on a subchronic

### MEPC 61/2/9 Annex, page 66

I:\MEPC\61\2-9.doc 

### rather than a chronic study, and (4) derivation of an RfD from the LOAEL rather than the NOAEL. A safety factor of 10 is typically applied for each of these uncertainties during the development of the RfD. Thus, the safety factor for an individual COPC could be as high as 10,000. In addition to these uncertainty factors, modifying factors between 0 and 10 may be applied to reflect additional qualit ative considerations (US EPA 1989).

12.2.4.3 Carcinogenic adverse health effects

The incremental lifetime cancer risk (ILCR) attributed to a carcinogen is calculated as a product of the daily intake (mg/kg-d) and the cancer slope factor (CSF). The US EPA's model of carcinogenesis assumes the relationship between exposure to a carcinogen and cancer risk is linear over the entire dose range, except at very high doses (US EPA 1989). This linearity assumes there is no threshold-of-exposure dose below which harmful effects will not occur. Because of this, carcinogenic effects are considered to be cumulative across age groups when considering lifetime exposures.

CSFs are upper-bound (95% upper confidence limit (UCL)) estimates of the increased cancer risk per unit dose, in which risk is expressed as the probability that an individual will develop cancer within his or her lifetime as the result of exposure to a given level of a carcinogen. All cancers or tumours are considered whether or not death results. This approach is inherently conservative because of the no-threshold assumption and the use of the 95% UCL of the estimated slope of dose versus cancer risk.

To identify oral RfDs and slope factors, the studies and approaches described by the US EPA in its Integrated Risk Information System (IRIS) were compared to the toxicological information reported in section 4 (Tables 11 to 13) of both this dossier and the dossier for Basic Approval. When no toxicity values are reported in IRIS, best professional judgment was used to develop values based on the data reported in Tables 11 to 13 in both this dossier and the dossier for Basic Approval.

12.2.4.4 Hypochlorous acid and hypobromous acid

The health effects associated with hypochlorite (salts of hypochlorous acids) have been studied primarily as it relates to its use as a disinfectant in drinking water. While various drinking water goals for disinfectants have been established by the US EPA, the World Health Organization (WHO), and the European Union (EEC), only the US EPA has identified an oral reference dose for chlorine: 0.1 mg/kg-day (US EPA 1994). This value, as reported in IRIS, is based on based on the NOAEL of 14 mg/kg-day for rats exposed to chlorine in drinking water for two years (NTP 1992a), as reported in Table 11 of the dossier for Basic Approval (Chronic Mammalian Toxicity). The US EPA (1994) applies a composite uncertainty factor of 100: 10 to account for interspecies extrapolation and 10 to account for the protection of sensitive subpopulations.

No toxicological information was found for hy pobromous acid, or the associated hypobromite salts. As previously reported, hypobromous acid is believed to be similar in toxicity to its chlorinated analogue, hypochlorous acid. Therefore, as indicated in the COPC selection (section 12.2.2), the Active Substance in the BalPure ® 

### BWMS is evaluated qualitatively as hypochlorous acid.

12.2.4.5 Total trihalomethanes

During land-based testing, the trihalomethane (THM) by-products detected in ballast water included bromoform (tribromomethane), dichlo robromomethane, and chlorodibromomethane. Although not detected in samples from land-based testing, chloroform is another THM for

### MEPC 61/2/9 Annex, page 67

I:\MEPC\61\2-9.doc 

### which toxicity data is available. The US EPA has identified oral reference doses for four of these THMs in IRIS, with values ranging from 0.01 mg/kg-day (chloroform; US EPA 2001b) to 0.02 mg/kg-day (bromoform [US EPA 1991a], dichlorobromomethane [US EPA 1991b], and chlorodibromomethane [US EPA 1991c]). The lowest (and therefore most conservative) value is from the study of beagles administered oral doses (15 or 30 mg/kg-day) of chloroform in capsules for 5 days/week over 7.5 years for which a LOAEL of 15 mg/kg/day for liver effects, as is reported in Table 11 (Chronic Mammalian Toxicity) of the dossier for Basic Approval. 1 

### The US EPA (2001b) derived the oral reference dose based on a modeled low benchmark dose (BMDL 10 

### ) of 1.0 mg/kg-day, and included a composite uncertainty factor of 100: 10 to account for extrapolation from animal data to humans and 10 to account for intrahuman variability (US EPA 2009). 2



### As reported in Table 13 "Summary of Data on Carcinogenicity" of the Basic Approval dossier either IARC or the US EPA has classified each of the four THMs as "probable" or "possible" human carcinogens. Based on the studies identified in Table 13 of the Basic Approval dossier, US EPA, in IRIS, has derived oral slope factors for bromoform (7.3 x 10 -3 

### per mg/kg-day; US EPA 1991a), dichlorobromomethane (6.2 x 10 -2 

### per mg/kg-day; US EPA 1991b), and chlorodibromomethane (8.4 x 10 -2 

### per mg/kg-day; 1991c) 3 

### . The highest value is the most conservative, therefore the oral slope factor for chlorodibromomethane is used to evaluate carcinogenic risks from THMs.

12.2.4.6 Total haloacetic acids

As described in section 2, haloacetic acid (HAA) by-products detected in ballast water discharge during land-based testing included bromochloracetic acid, mono- and dichloroacetic acids, and mono- and di- and tribromoacetic acids, and dibromochloroacetic. Of these, the US EPA (2003) has identified an oral reference dose in IRIS for only dichloroacetic acid, however, this value is based on a subchronic (90 day study), which is not optimal for the evaluation of chronic effects. As described above, a chronic effects level can be developed based on the NOAELs or LOAELs reported for chronic toxicity studies in Table 11 of the Basic Approval. In section 11.3 of this dossier, no reported NOAELs or LOAELs could be located for the additional substances. The available NOAELs identified for HAAs in the Basic Approval tables range from 3.5 mg/kg/day for monochloroacetic acid (EU 2005) to 40 mg/kg/day for trichloroacetic acid (IPCS 2000a); all studies are based on effects on rodents, therefore a composite uncertainty factor of 100 (10 to account for extrapolation from animal data to humans and 10 to account for intrahuman variability) is appropriate for the determination of a reference dose from any of these studies. The lowest (and therefore most conservative) NOAEL-based calculated value is for monochloroacetic acid – 0.034 mg/kg/day. The LOAELs identified for HAAs range from 2 mg/kg/day for dibromoacetic acid (NTP 2007) to 40 mg/kg/day for dichloroacetic acid (IPCS 2000a); all studies are based on effects on rodents, therefore a composite uncertainty factor of 1000 (10 to account for the use of a LOAEL instead of a NOAEL, 10 to account for extrapolation from animal data to humans, and 10 to account for intrahuman variability) is appropriate for the det ermination of a reference dose from any of these studies. The lowest (and therefore most conservative) LOAEL-based value is for dibromoacetic acid – 0.002 mg/kg/day. Because the LOAEL-based value results in the lowest reference dose, it is used to evaluate non-carcinogenic risks from HAAs.

1 IRIS reference doses for bromoform and chloro dibromomethane are based on subchronic studies associated with the same NTP studies (1989 and 1985, respectively) cited in Table 11 of the dossier for Basic Approval. The IRIS reference dose for dichlorobromomethane is based on the NTP (1987) chronic LOAEL of 25 mg/kg/d cited in Table 11 of the dossier for Basic Approval.

2 A similar oral reference dose resu lted from the NOAEL/LOAEL approach.

3 USEPA has determined that while oral exposure to chloroform may cause cancer, the reference dose of 0.01 mg/kg-day is considered to be protective against cancer risk.

### MEPC 61/2/9 Annex, page 68

I:\MEPC\61\2-9.doc 

### As reported in Table 13 (Summary of Data on Carcinogenicity) of this and the dossier for Basic Approval only dichloroacetic acid, dibromoacetic acid, and trichloroacetic acid have been classified as either "probable" or "possible" human carcinogens. 4 

### However, IRIS includes oral slope factors for only dichloroacetic acid (0.05 per mg/kg-day; US EPA 2003), therefore this value is used to evaluate carcinogenic risks from HAAs. It is noted that while no cancer slope factor has been developed for the remaining HAAs, the effects levels reported in Table 13 of the dossier for Basic Approval are up to 20 times lower for dibromoacetic acid ( ≥ 4 mg/kg/day) than those reported for dichloroacetic acid (84 mg/kg/day). Therefore, some uncertainty exists in the carcinogenic evaluation of HAAs; specifically carcinogenic risks associated with dibromoacetic acid, the dominant residual HAA measured in ballast water (see Tables 22 and 23) may be underestimated.

12.2.4.7 2,4,6-Tribomophenol

As shown in Tables 11 and 13, no long-term exposure or carcinogenic studies on brominated phenols have been identified (CICADS 66 2005). With respect to carcinogenicity, 2,4,6-tribromophenol has not been classified (NTP 2009, IARC 2009). However, given the very low levels of 2,4,6-TBP detected (two orders of magnitude lower than other COPCs; see Table 30) and the presence of this chemical in s ource water, any risks associated with this
chemical as a result of BalPure ® 

### BWMS are expected to be very low.

12.2.4.8 Sodium bisulfite

The US EPA has not developed an oral reference dose for sodium bisulfite inclusion in IRIS. However, as reported in Table 11 "Chronic Mammalian Toxicity" in the application dossier for Basic Approval, The Health Council of the Netherlands identified a NOAEL of 72 mg/kg-day for rats fed up to 20,000 mg/L sodium bisulfite, based on local effects (blood in feces; hyperplastic changes of gastric epithelium) (2005). In the absence of other information, an oral RfD can be calculated by applying a composite uncertainty factor of 100, 10 to account for interspecies extrapolation and 10 to account for intrahuman variability, to the NOAEL (72 mg/kg-day). This results in an oral RfD of 0.72 mg/kg-day.

As reported in Table 13 "Summary of Data on Carcinogenicity" in the application dossier for Basic Approval, sodium bisulfite is not classifi able as to its carcinogenicity, therefore no oral cancer slope factor is available.

As shown in Table 33, reference doses were identified for all COPCs except 2,4,6-tribromophenol. Cancer slope factors are available for only THMs and HAAs; therefore carcinogenic effects can be evaluated for only these three COPCs.

Table 33: Summary of Toxicity Criteria

Substance Oral Reference Dose (mg/kg/day) Oral Cancer Slope Facto r (per mg/kg-day)
Hypochlorous Acid 1.00E-01 (chlorine) NC

THMs 1.00E-02 (chloroform)* 8. 40E-02 (chlorodibromomethane)

HAAs 2.00E-03 (dibromoacetic acid ) 5.00E-02 (dichloroacetic acid)

2,4,6-Tribromophenol NC NC

Sodium bisulfite 7.20E-01 NC

* Although chloroform was not detected in the land-based testing of the Balpure ® system, it was identified as having the most conservative oral reference dose and to maintain the health-protectiveness of the ev aluation, is retained here.
NC = No criteria.

4 As indicated in Table 13, NTP (2009) reports “Clear evidence of carcinogenic activity” in animals for

bromochloroacetic acid.

### MEPC 61/2/9 Annex, page 69

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### 12.2.5 Risk characterization

Risk characterization, the final step in the risk assessment process, combines data from the hazard identification, health effects assessment, and exposure assessment to estimate the potential carcinogenic and non-carcinogenic effects of COPCs over the applicable duration of exposure. Despite quantification, it is believed that the actual potential health risks are very low because of the low potential of exposure to chemicals associated with the BalPure ®


### BWMS. Risks presented below should be considered worst-case estimates.

Risks presented herein differ from the application dossier for Basic Approval in two ways: (1) risks for technicians or others who may be exposed during ballast water discharge sampling are evaluated quantitatively, and (2) risks to receptors previously evaluated for potential exposure to treated ballast water discharge have been revised using the land-based testing results to estimate exposure.

12.2.5.1 Acceptable risk levels

The risk that is acceptable is very much dependent on site-specific characteristics that include: the number of people potentially expos ed, the likelihood of exposure, the chemicals driving the risk, and the decisions of risk man agers. The incremental lifetime cancer risk (ILCR) is compared to a range of acceptable probabilities to determine whether the potential risk poses an unacceptable health threat. The US EPA directive, Role of the Baseline Risk Evaluation in Superfund Remedy Selection Decisions (US EPA 1991a), states that action is generally not warranted at a site when the cumulative carcinogenic risk for current and future

land use is less than 1 x 10 -4 

### and the cumulative non-carcinogenic hazard index (HI) is less than 1.0. The level of non-cancer hazard concern increases as the HI increases above unity, although the two are not linearly related (US EPA 1989). The US EPA uses a potential
excess individual lifetime cancer risk of 1 x 10 -6 

### (1 in 1,000,000) as a point of departure for risk management actions.

12.2.5.2 Quantitative estimate of potential risks to STDN BalPure ® 

### technicians

Table 34 summarizes the risks quantified for the BalPure ® 

### Technician who may be exposed to concentrated hypochlorous acid (generated concentration of 0.1%) during maintenance activities or to the 38% sodium bisulfite solution during chemical resupply. Neither hypochlorous acid nor sodium bisulfite is cl assifiable with respect to carcinogenicity, therefore cancer risks are not reported below. The non-cancer hazard of 0.3 is well below the level of concern (1.0); use of personal protective equipment (PPE) and safe chemical handling procedures will further reduce any potential exposures and associated effects.

Table 34: Summary of Cancer Risks and Non-cancer Hazards for

BalPure ® 

### Technicians

Substance Cancer Risk Non-cancer Hazard
Ingestion Dermal Total Ingestion Dermal Total
Hypochlorous Acid NC NC NA 0.0049 0.00032 0.0052

Sodium Bisulfite NC NC NA 0.26 0.017 0.28

TOTAL NA 0.3

NA = not applicable, NC = no criteria.

### MEPC 61/2/9 Annex, page 70

I:\MEPC\61\2-9.doc 

### 12.2.5.3 Quantitative estimate of potential risks to STDN BalPure ® 

### technicians (or others) during ballast water discharge sampling

Table 35 summarizes the risks quantified for the BalPure ® 

### Technician, or other worker, who may be exposed to COPCs in ballast water during discharge sampling, based on land-based testing maximum COPC concentrations. Hypochlorous acid, 2,4,6-tribromophenol, and sodium bisulfite are not classifiable with respect to carcinogenicity, therefore cancer risks are reported for only THMs and HAAs. The total estimated cancer risk of 8 x 10 -8 

### (8 in 100,000,000) is far below the US EPA point of departure of 1 x 10 -6 

### (1 in 1,000,000). The total non-cancer hazard, 0.002, is several orders of magnitude below the target level of 1.0.

Table 35: Summary of Cancer Risks and Non-cancer Hazards for BalPure ® 

### Technicians (or others) – Ballast Water Discharge Sampling

Substance Cancer Risk Non-cancer Hazard
Ingestion Dermal Total Ingestion Dermal Total
Hypochlorous Acid NA NC NA NA 0.00018 0.00018

THMs NA 6.3E-08 6.3E-0 8 NA 0.00053 0.00053

HAAs NA 1.7E-08 1.7E-08 NA 0.0012 0.0012
2,4,6-Tribromophenol NA NC NC NA NC NC

Sodium Bisulfite NA NC NC NA 0.000010 0.000010

TOTAL 8E-08 0.002

NA = not applicable, NC = no criteria.



### 12.2.5.4 Quantitative estimate of potential risks to ship's crew or dock workers

Table 36 summarizes the risks quantified for ship's crew or dock workers who may be exposed to COPCs in ballast water from spray drift, based on land-based testing maximum COPC concentrations. Hypochlorous acid, 2,4,6-tribromophenol, and sodium bisulfite are not classifiable with respect to carcinogenicity, therefore cancer risks are reported for only
THMs and HAAs. The total estimated cancer risk of 2 x 10 -9 

### (2 in 1,000,000,000) remains essentially unchanged from that estimated in the Basic Approval dossier, and is far below the US EPA point of departure of 1 x 10 -6 

### . The total non-cancer hazard, 0.00004, is only slightly higher than reported in the previous risk assessment and remains many orders of magnitude below the target level of 1.0.

Table 36: Summary of Cancer Risks and Non-cancer Hazard for Ship's Crew/Dock Workers

Substance Cancer Risk Non-cancer Hazard
Ingestion Dermal Total Ingestion Dermal Total
Hypochlorous Acid NA NC NA NA 0.0000035 0.0000035

THMs NA 1.3E-09 1.2E-0 9 NA 0.000010 0.000010

HAAs NA 3.2E-10 3.2E-1 0 NA 0.000023 0.000023
2,4,6-Tribromophenol NA NC NC NA NC NC

Sodium Bisulfite NA NC NC NA 0.00000020 0.00000020

TOTAL 2E-09 0.00004

NA = not applicable, NC = no criteria.

### MEPC 61/2/9 Annex, page 71

I:\MEPC\61\2-9.doc 

### 12.2.5.5 Quantitative estimate of potential risks to the general public (beachgoers)

Table 37 shows cancer risks to beachgoers who may swim in the vicinity of recently discharged ballast water associated with the BalPure ® 

### BWMS, based on land-based testing maximum COPC concentrations (assumed to be instantly diluted 100-fold). Hypochlorous acid, 2,4,6-tribromophenol, and sodium bisulfite are not classifiable with respect to carcinogenicity, therefore cancer risks are repo rted for only THMs and HAAs. The total estimated cancer risk is very low at 3 x 10 -8 

### (3 in 100,000,000), is slightly lower than estimated in the Basic Approval dossier and is far below the US EPA point of departure of 1 x 10 -6



### .

Table 37: Summary of Cancer Risks for the General Public

Substance Cancer Risk *

Ingestion Dermal Total
Hypochlorous Acid NC NC NA

THMs 1.0E-08 1.7E-08 2.7E-08

HAAs 2.7E-09 4.4E-09 7.1E-09
2,4,6-Tribromophenol NC NC NC

Sodium Bisulfite NC NC NC

TOTAL 3E-08

Cancer risk is age-adjusted, assumi ng 6 years of exposure as a child and 24 years as an adult.
NC = no criteria.



### Non-cancer hazards for the general public, which are summarized in Table 38, also are very low; 0.0007 for children and 0.0002 for adults. Although slightly higher than reported in the Basic Approval dossier, these non-cancer hazar ds remain many orders of magnitude below the target level of 1.0.

Table 38: Summary of Non-cancer Hazards for General Public

Substance Adult Non-cancer Hazard Child Non-cancer Hazard
Ingestion Dermal Total Ingestion Dermal Total
Hypochlorous Acid 0.000039 0.000014 0.000053 0.00018 0.000024 0.00021

THMs 0.000017 0.000040 0.0000 57 0.000077 0.000069 0.00015

HAAs 0.000037 0.000090 0.00013 0.00017 0.00015 0.00033
2,4,6-Tribromophenol NC NC NC NC NC NC

Sodium Bisulfite 0.0000022 0.00000078 0.0000030 0.000010 0.0000013 0.000012

TOTAL 0.0002 0.0007

NC = no criteria



### 12.2.5.6 Semi-quantitative evaluation of potential risks from inhalation

The risk estimates reported in Tables 34 to 38 do not include inhalation of COPCs in indoor or outdoor air. While significant volatilizati on of COPCs from ballast water into indoor or outdoor air is not anticipated, some exposure to COPCs in air could occur. The most likely operation that could result in exposure to COPCs in air is during ballasting, when air in the ballast tanks is vented to the atmosphere as water is brought into the tanks. If the ship's crew is present during this operation, they could be exposed to residual THMs in vent air, since these disinfection by-products are both volatile and hydrophobic. Although concentrations of THMs in vent air have not been measured, worst-case estimates of air concentrations can be made based on maximum ballast water THM concentrations (see section 11.3) and the

### MEPC 61/2/9 Annex, page 72

I:\MEPC\61\2-9.doc 

### appropriate Henry's Law constants (the ratio of the aqueous-phase concentration of a chemical to its equilibrium partial pressure in the gas phase). Because ve nt air will be immediately mixed into the surrounding atmosphere, the air concentration estimates are also adjusted for dilution into ambient air by dividing by a factor 10. As a conservative evaluation of the inhalation exposure pathway, Table 39 summarizes these data (updated to reflect land-based test results), and compares the revised estimated air concentrations to U.S. OSHA Permissible Exposure Levels (PELs).

Table 39: Estimated Concentrations of THMs in Vent Air and Comparisons to PELs

Substance Basic Approval

Dossier
Maximum

Residual
Ballast Water
Concentration (μg/L) Final Approval

Dossier
Maximum

Residual
Ballast Water
Concentration (μg/L) Henry's

Law
Constant (unitless) Final Approval
Dossier

Estimated
Conc. in

Air (mg/m 3 )* Air Exposure

Limit (mg/m 3 )** Air
Concentration

Exceeds Exposure Limit?

THMs

Bromoform 1050 810 0.0218 1.8 5 No

Chloroform 53 Not detected 0.150 Not

detected 240 No

Chlorodibromomethane 157 33 0.0320 0.11 NA NA

Dichlorobromomethane 90 1.5 0.0654 0.0098 NA NA

NA = Not Available. * Estimated based on Henry's Law constant at 25°C, and divided by a factor of 10 for dilution into ambient air. ** U.S. Department of Labor, 2009. Occupational Health and Safety Administration, Permissible Exposure Limits (PEL).



### Actual air exposures will depend on proximity to vent outlets, atmospheric conditions (wind), as well as the duration of ballasting. Because the THMs in vent air would quickly dissipate into the atmosphere, it is anticipated that air exposures will decrease as distance to the ballast water increases; therefore potential air exposures for dock workers and the general public would be even less than those for the ship's crew. Based on this assessment of THMs in vent air as a result of concentrations in ballast water, there is no evidence for the potential of adverse health effects to the ship's crew, dock workers, or the general public.

12.2.6 Risk assessment conclusions

Overall risk findings from the application dossier for Basic Approval remain unchanged: the health risks to all receptors from the BalPure ® 

### BWMS under normal operating conditions are very small and well within acceptable levels. Even an STDN technician, exposed to concentrated sodium bisulfite during a spill dur ing chemical resupply, and who is wearing no PPE – an unlikely scenario – would have low health risk. Cancer risk and non-cancer hazards for the general public/beachgoers are well below levels of concern; actual risks to these receptors are expected to be even lower, as they are unlikely to be repeatedly exposed to treated ballast water as assumed in this risk evaluation. Since the risk assessment only evaluated direct exposure via ingestion and dermal contact with chemicals or ballast water, as these were considered the most relevant pathways, further semi-qualitative evaluation of the inhalation pathway was performed for the volatile THMs. This assessment demonstrated that conservative concentrations of airborne THMs generated by a release of ballast water were well below occupational exposure limits.

### MEPC 61/2/9 Annex, page 73

I:\MEPC\61\2-9.doc 

### 12.3 Risks to the aquatic environment

Potential risk to the aquatic environment as a result of the BalPure ® 

### BWMS was evaluated in several regards. The substances potentially present in treated/neutralized ballast water discharge were evaluated with respect to aquatic ecotoxicity, bioaccumulation potential and environmental persistence and the whole effluent was evaluated for discharge ecotoxicity. The Basic Approval dossier (MEPC 60/2/9) presented data from pilot scale studies, while this document presents data generated during land-based testing of the full commercial scale

BalPure ® 

### system. Additionally, emission scenarios were simulated using the MAMPEC model to generate meaningful PEC values to allow for a risk assessment with the PEC/PNEC ratio

method.

Direct ecotoxicity evaluation of whole effluent from the BalPure ® 

### system indicates that the potential risks to the aquatic environment are ve ry low. The acute and chronic WET testing data indicate that 100% whole effluent did not have toxic effects on five of the six species tested (Tables 3 and 5). For one species, Acartia tonsa , an effect was observed in one of four acute tests with a low salinity sample. In this sample, a moderate effect was observed in the two highest test concentrations (100% and 32% sample), resulting in a NOEC of 18% volume (Grontmij|AquaSense, 2009). It is important to note that during tests with Acartia moderate effects were also noted in a control (untreated, NIOZ harbour water) sample (EC 20 

### of 58% sample) (Grontmij|AquaSense, 2009). As explained in sections 11.4 and 11.13 above, a possible explanation for the moderate toxic effect in the treated and control samples is the presence of Phaeocystis, an algal species known to be abundant in the NIOZ harbour

and which excretes allelochemicals. All other acute and chronic tests with Acartia, as well as the five other species tested, demonstrate that 100% whole effluent sample had no toxic effect, indicating that the NOEC of 18% (Table 3) is an outlying data point.

The conclusion of low potential risk to the aquatic environment is supported by the results of worst-case discharge scenarios simulated with the MAMPEC model. By employing the modelling approach described in section 11.8.1, it is important to note the layers of conservatism applied. First, MAMPEC assumes continuous discharges (leaching from antifoulants), rather than intermittent discharges (ballast water). Second, the physical dimensions of the "OECD Commercial Harbour" configuration are smaller and tidal flushing is less, yet the ballast water discharge rate for the whole Port of Rotterdam was used. Environment B builds onto the worst case emission scenario with a smaller tidal exchange flow rate, minimizing the harbour exchange percentage due to flushing. These elements result in overly conservative, rather than realistic, PEC values. Lastly, in derivation of PNEC values the lowest effect concentrations and highest appropriate assessment factors have been used (see section 11.9). All PEC/PNEC ratios, even when calculated using PEC values generated in the very conservative "reduced flushing" Environment B, are well below 1 and can be considered as protective of the aquatic environment. Therefore, no further assessment of direct toxic effe cts is necessary as risks to the aquatic environment are not expected from the use of the BalPure ® 

### system.

13 ASSESSMENT REPORT

The substances associated with the BalPure ® 

### system were evaluated for a variety of endpoints, including ecotoxicity, bioaccumulation, and persistence in the environment. Additionally, STDN's application dossier for Basi c Approval (MEPC 60/2/9) included a full assessment (including ship safety and human health) with respect to the onboard storage of sodium bisulfite and the onboard generation of sodium hypochlorite. During the assessment of potential risks related to the BalPure ® 

### system, a variety of reputable sources were consulted to gather test data and conduct the assessments required. These sources include, but are not limited to the WHO, IPCS, OECD and US EPA. Information was also gathered from published independent research, which in most cases is peer-reviewed by others with

### MEPC 61/2/9 Annex, page 74

I:\MEPC\61\2-9.doc 

### similar levels of expertise. Further, reputable laboratories that utilize recognized testing methods and appropriate quality control measures were commissioned for the toxicological and analytical evaluations of ballast water discharge. Based on these facts, the level of uncertainty associated with this assessment is low.

Aquatic toxicity was established as being the most likely potential risk to the aquatic environment. Because TRO (as Cl 2 

### ) is neutralized prior to discharge, the DBPs potentially present in treated/neutralized ballast water discharge are the most important to consider for this evaluation. In regards to aquatic ecotoxicity, the existing database for chronic endpoints is limited for many of the THMs and HAAs. As such, the acute database, which is more complete, was utilized for some substances. The evaluation of the chemical and physical properties of all chemicals relevant to the BalPure ® 

### system suggests that bioaccumulation, sediment adsorption, or environmental persistence is not expected to occur. Further, none of
the chemicals met all three criteria to be classified as PBT substances.

Whole effluent toxicity (WET) testing was performed with treated/neutralized samples drawn from the land-based test set-up. With the exception of one acute test with Acartia tonsa, all other acute and chronic discharge toxicity tests indicate no aquatic toxicity. Because only one in eight tests with Acartia indicated moderate toxicity, and toxic effects were also observed in a control sample during testing with this species, the NOEC of 18% sample was likely to have been caused by compounds excreted by the algal species Phaeocystis. All other tests for the five remaining species of aquatic organisms resulted in effect
concentrations of ≥ 100% sample.

Lastly, two different emission scenarios (Environments A and B) were simulated with MAMPEC using the median DBP concentrations in ballast discharge. The resulting PEC values allowed for calculation of PEC/PNEC ratios to estimate aquatic risk. All calculated ratios for the substances measured in ballast water discharge are well below 1. Based on this assessment, no potential risks as a result of ballast water discharge from the BalPure ® 

### system are anticipated.

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### MEPC 61/2/9 Annex, page 79

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