I:\MEPC\57\2-8.doc For reasons of economy, this document is pr inted in a limited number. Delegates are kindly asked to bring their copies to mee tings and not to request additional copies. INTERNATIONAL MARITIME ORGANIZATION

IMO 

# E

MARINE ENVIRONMENT PROTECTION COMMITTEE 57th session Agenda item 2 MEPC 57/2/8 26 December 2007 Original: ENGLISH

HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Basic Approval of the ballast water management system using “TG Ballastcleaner and TG Environmentalguard” as Active Substances (Toagosei Group)

Submitted by Japan

SUMMARY
Executive summary: This document contains non-confidential information for Basic Approval of the ballast wa ter management system using “TG Ballastcleaner” and “TG Environmentalguard” as Active Substances developed by Toagosei Group in accordance with the Procedure for approval of ballast water management systems that make use of Active Substance (G9) adopted by resolution MEPC.126(53). Relevant documents and an application dossier will be provided to Marine Environment Division of th e Organization for review by the GESAMP-Ballast Water Working Group.

Action to be taken: Paragraph 5

Related documents: BWM/CONF/36; MEPC 53/24/Add.1 and BWM.2/Circ.12

Introduction

1 Regulation D-3.2 of the Ballast Water Ma nagement Convention (BWM Convention) requires that ballast water management systems that make use of Active Substances to comply with the Convention shall be approved by IMO based on a procedure developed by the Organization.

2 MEPC 53 adopted the Procedure for approval of ballast water management systems that make use of Active Substances (G9) by resolu tion MEPC.126(53). Section 8 of Procedure (G9) sets out the methodology to be followed for the approval of such systems and requests IMO to establish a Technical Group (t he GESAMP-Ballast Water Working Group) to review the proposals submitted by Members and report to the Organization on its findings.

3 According to BWM.2/Circ.12, proposals for approval of ballast water management systems that make use of Active Substances are to be submitted to Marine Environment Division of the Organization to be reviewed by the GESAMP-Ballast Water Working Group. In the meantime, a document on the proposal for approval containing all the non-confidential dataMEPC 57/2/8 - 2 -

I:\MEPC\57\2-8.doc related to the respective ballast water management system that makes use of Active Substances needs to be submitted to MEPC 57.

4 Japan therefore submits the non-confidential part of the applicant’s dossier in the annex to this document to the Organization for evaluatio n according to Procedure (G9). The complete dossier will be made available to the experts of the GESAMP-B allast Water Working Group with the understanding of conf idential treatment.

Action requested of the Committee

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

***MEPC 57/2/8

I:\MEPC\57\2-8.doc ANNEX

NON-CONFIDENTIAL INFORMATION ON THE BALLAST WATER MANAGEMENT SYSTEM USING “TG BALLASTCLEANER AND TG ENVIRONMENTALGUARD” AS ACTIVE SUBSTANCES DEVELOPED BY TOAGOSEI GROUP (JAPAN)

SUMMARY

The Toagosei Group (TG Corporation, Toagosei Co. Ltd. and Tsurumi Soda Co. Ltd.) has developed a chemical system for the treatment of ships’ ballast water and sediments. The system minimizes or completely eliminates the risks that the transfer of harmfu l aquatic organisms and pathogens poses to environment, human healt h, property or resources. It also avoids the undesired effects of the Active S ubstances used for disinfection.

The framework of this ballast water treatment system that uses two kinds of Active Substances is composed of the following.

Firstly, while ballasting, most of aquatic organisms and large si ze suspended particles which are larger than 50 μm in pumped up seawater are removed by high performance filters and returned to the sea in backwash water of the filters. Secondly, TG Ballastcleaner (sodium hypochlorite) is added into the turbulent flow in the pipe in orde r to kill all the living aquatic organisms left in ballast water. Thirdly, while deballasting, residual chlorine contained in the disinfected ballast water is reduced and eliminated by adding TG E nvironmentalguard (sodium sulfite) in order to protect marine habitats in the surrounding seawater where the trea ted ballast water is discharged.

This is a groundbreaking chemical system in the senses of effective disinfection and harmlessness to the environment in three aspects: (1) it returns most of aquatic organisms to their natural habitats by filter backwash; (2) it uses very effective disinfectant, sodium hypochlorite, during ballasting; an d (3) it completely eliminates residual chlorine by adding sodium sulfite during deballasting st age. The concept of this chemi cal system is outlined in Fig.1.

Fig.1 Concept of the chemical system
Active Substances, Other Components and Relevant Chemicals generated by the reactions of the Active Substances, which are related to this syst em, are shown in Table 1. Screening results for risk assessments and examining mammalian t oxicity are also show n in this table. NaClO ... TG Ballastcleaner TG Environmentalguard

Ballast

NaClO
Na 2 SO 3 Na 2 SO 4

Seawater
Freshwater BALLASTING DEBALLASTING

Disinfected Ballast Water Treated Ballast Water Ballast Line

Water Environment NaClO Na 2 SO 3

Filter

Back Wash WaterMEPC 57/2/8 ANNEX Page 2

I:\MEPC\57\2-8.doc Table 1 Screening results for risk assessments and mammalian toxicity

Required investigation Classifi -cation Chemical substance
Risk assessment Mammalian toxicity Reason for exclusion

Trade Name: TG Ballastcleaner AS Sodium hypochlorite X O Reduced by aquatic organisms, organic matter and sodium sulfite OC Sodium chloride X X Conc. is very low compared with natural conc. in seawater
OC Sodium hydroxide X X Becomes salt and water (pH is neutral) RC Residual chlorine X N/A Reduced by sodium sulfite RC Chloroform O N/A RC Bromodichloromethane O N/A RC Dibromochloromethane O N/A RC Bromoform O N/A RC Sodium bromate O N/A RC Monochloroacetic acid O N/A RC Dichloroacetic acid O N/A RC Trichloroacetic acid O N/A
RC Bromochloroacetic acid X N/A Generated in trace No regulations such as WHO
RC Bromoacetic acid O N/A
RC Dibromoacetic acid O N/A
RC Other haloacetic acids X N/A Not detected
RC Haloacetonitriles X N/A Not detected
Trade Name: TG Environmentalguard
AS Sodium sulfite O (short only ) O (acute only ) Becomes sodium sulfate reacting with residual chlorine and dissolved oxygen
OC/RC Sodium sulfate X O Very slight compared with natural concentration in seawater AS: Active Substance, OC: Other Component, RC: Relevant Chemical, N/A: Not Applicable

From the above results, chemical substances to be asse ssed for their effects on aquatic organisms are the following 11 chemical species:

sodium sulfite (acute toxicity only), sodium bromate, chloroform, bromodichloromethane, dibrom ochloromethane, bromoform, monochloroacetic acid, dichloroacetic acid, trichlor oacetic acid, bromoacetic ac id and dibromoacetic acid.MEPC 57/2/8 ANNEX

Page 3

I:\MEPC\57\2-8.doc Chemical substances to be examined for mamm alian toxicity are the following three chemical species:

sodium hypochlorite, sodium sulfite and sodium sulfate.

The effect of dissolved oxygen (DO) decrease wh ich is induced by the reaction with sodium sulfite is examined, and it is found to be quite minute and not to affect the environment.

Toxicity tests and risk assessment were perfor med in order to evalua te the effects on the environment posed by the discharging of treated ba llast water when using this chemical system.

.1 Results of the toxicity te sts using three types of aqua tic organisms are as follows:

(a) No acute toxicity was observed for all the types of aquatic organisms.

(b) No chronic toxicity was obs erved for fish and crustacean.

(c) Slight effect on the growth rate of algae was observed, but the growth rate was not affected if the treated ballast water was diluted more than 5.24 fold.

.2 The assessment by PBT criteria was performed. There are no chemical substances which fall under the three categories, and it proceeds to risk assessment.

.3 Risk assessments were performed by m easuring the concentrations of the above described eleven chemical substances in the simulated ballast water and using the estimated dilution factors of PEC cal culated using the MAM-PEC model. The results of PEC/PNEC examinati on are shown in Table 2 and Table 3.

Table 2 PEC/PNEC ratios for six chem ical substances using MAM-PEC model

Chemical substance PEC / PNEC
Chloroform Freshwater: 0.052, seawater: 0.025
Bromoform Freshwater: 0.11, seawater: 0.46
Monochloroacetic acid 0.28
Trichloroacetic acid 0.98
Bromoacetic acid 0.61
Sodium sulfite 0.0013 (short)MEPC 57/2/8 ANNEX Page 4

I:\MEPC\57\2-8.doc Table 3 PEC/PNEC ratios for fi ve chemical substances using the conservative dilution factor

Chemical substance Dilution factor PEC / PNEC
Sodium bromate 1/58 0.005
Bromodichloromethane 1/58 0.004
Dibromochloromethane 1/58 0.006
Dichloroacetic acid 1/58 0.0001
Dibromoacetic acid 1/58 0.014

After the above considerations, the ballast wa ter treated with the TG Ballastcleaner and TG Environmentalguard is deemed to have no effect on the surrounding water and aquatic organisms.

Studies in the physical and chemical properties of the two Active Substances have shown that this chemical system does not threaten the structural integrity of ships or the health and safety of the ship’s personnel when they are properly ba sed on the prepared operating instructions.

1 INTRODUCTION

Aquatic organisms artificially transported to other regions beyond their natu ral areas of distribution disrupt the ecosystems of those regions. Invasive sp ecies are introduced not only as a result of fishery practices that allow benthic organisms and peri phyton such as biva lves, starfish, balanomorpha and seaweed to be transported with marine products intended for feed or for stock. They are also introduced by ships to which they attach themselves or in whose ballast water they are carried.

The International Maritime Organi zation took up this issue in the latter half of th e 1980s and in February 2004 adopted the International Conventi on for the Control and Management of Ships’ Ballast Water and Sediments, which regulates the ma nagement of ballast water. It articulated the direction of efforts for this problem by specifyin g mandatory to adopt an approved ballast water treatment management system (such as ballast wa ter treatment equipments) for all ships engaging in international voyages.

Toagosei Group (TG Corporation, Toagosei Co. Ltd. and Tsurumi Soda Co. Ltd.) therefore utilized a widely used disinfectan t to kill invasive species in ballast water. It is effective yet inexpensive chemical compound, sodium hypochl orite (trade name: TG Ballastcleaner). The disadvantage of this concept is that the discharged ballast water containing residual chlorine derived from sodium hypochlorite will adversely a ffect aquatic organisms in the water where the discharged ballast water is r eceived. Residual chlorine has been much concerned in sewage treatment and electrical power plants that use chlorine to disinfectant.

To avoid this adverse effect, a reducing agent was conceived to be added to the disinfected ballast water in order to reduce and eliminate residual chlorine completely. For this purpose Toagosei Group selected a reducing agent, sodium sulfite (trade name: TG Environmentalguard) that is an approved food additive.MEPC 57/2/8 ANNEX

Page 5

I:\MEPC\57\2-8.doc 2 OUTLINE OF CHEMICAL SYSTEM

This chemical system uses, as the first Active Substance, sodium hypochlorite which is the main ingredient in TG Ballastcleaner as a disinfectan t to kill aquatic organisms, and uses, as the second Active Substance, sodium sulfite which is the main ingredient in TG Environmentalguard as an agent to eliminate residual chlorine from the ballast water which is disinfected with TG Ballastcleaner (hereafter it is described as disinfected ballast water) because of its reducing ability. This system operates as follows:

.1 When ballast water is loaded on board using a ballast pump, a high-performance filter is used to remove organisms and sediment over a certain size before TG Ballastcleaner (containing sodium hypochl orite) is injected into the ballast water. The organisms which are filtered out are sent back to their natural habitats in the backwash water of the filter.

.2 TG Ballastcleaner is supplied from a storage tank to the ballast line at the prescribed addition ratio of 0.024% for seawater. This amount yields a free available chlorine (hereafter it is descri bed as FAC) concentration of 30 mg/l when the agent contains a 12% of FAC.

.3 TG Environmentalguard is supplied from a storage tank to the de ballast line at the prescribed addition ratio of 0.021% for seawater. This amount yields sodium sulfite concentration of 22 mg/l when the agent contains a 10% of sodium sulfite.

.4 To operate this system efficiently, the ch emical agents are desi gned to be added in turbulent flow regions for complete mixing.

Total treatment system with 250 m 3 /h capacity using this chemical system, filtration and cavitation generation device has been already te sted for two years. The system shows good performances and the several ope rational parameters are successf ully obtained as a complete ballast water management system. Developmen t of the injection control system of the “Active Substance” has been done in order to minimize the consumption of TG Ballastcleaner and TG Environmentalguard aiming at the applicati on for the Final Approval of this total system.

2.1 Disinfection process

TG Ballastcleaner, whose main ingr edient is sodium hypochlorite, is injected into the ballast line and the disinfected ballast water flows into the ship’s ballast tanks, where aquatic organisms are killed just after the injecti on and during the ship’s voyage.

2.2 Reduction process of residual chlorine

To prevent that the residual chlorine in the discharged ballast water kills local aquatic life, reproduction and finally disrupting the ecosyst em, TG Environmentalguard, which mainly consists of sodium sulfite as its “Active Substance”, is mixed into the disinfected ballast water to reduce the residual chlorine before the ballas t water is discharged. Residual chlorine in disinfected ballast water is comp letely eliminated and become harmless because of this process.

The excess of sodium sulfite becomes sodium sulfate by reacting w ith dissolved oxygen. Although a portion of dissolved ox ygen in the surrounding water re ceiving the treated ballast water decreases immediately after the ballast wa ter is discharged, environmental effects areMEPC 57/2/8 ANNEX Page 6

I:\MEPC\57\2-8.doc unlikely to exist because the oxygen is quickly supplied from the atmosphe re to surface water. The environmental effects of this method of removi ng residual chlorine have been examined near sewage-processing plants that empty sewage effl uent into Lake Michig an. The preservation of the quality of the water region was demonstrated using aquatic organisms as the benchmark (A.M.Beeton, 1976).

3 GENERAL REQUIREMENTS

3.1 Identification

3.1.1 Screening of “Active Substances”, “O ther Components” and “Relevant Chemicals”

TG Ballastcleaner contains sodium hypochlorite as its Active Substance, and it also contains sodium hydroxide and sodium chloride as Other Components which are remaining in the product. Using sodium hypochlorite generates or may generates by-products, their by-products are designated as Relevant Chemi cals, which include hypochlorous acid, hypobromous acid, sodium hypobromite, sodium bromate, chloramine, tr ihalomethanes, haloacetic acids and haloacetonitriles.

Another chemical agent, TG Environmentalguard contains sodium sulfite as its Active Substance and sodium sulfate as an Other Component which is remaining in the product. Sodium sulfate is also designated as a Relevant Chemical because it is generated when sodi um sulfite reacts with residual chlorine and dissolved oxygen in the disinfected ballast water.

Relevant Chemicals are selected from chemical substances which WHO and others enumerate as concerned chlorine disinfection by-products, and chemical substa nces which Robert L. Jolly et al. enumerate in “Water Chlorination Environmenta l Impact and Health Effects volume 1 to 5” with relation to power station cooling water in add ition to chlorine disi nfection by-products.

3.1.2 Identification of “Active Substan ces”, “Other Components” and “Relevant Chemicals”

Identification results on TG Ballastcleaner (s odium hypochlorite) and TG Environmentalguard (sodium sulfite) as “Active Substances” ar e listed in Tables 3.1.2.1 and 3.1.2.2, respectively.MEPC 57/2/8 ANNEX

Page 7

I:\MEPC\57\2-8.doc Table 3.1.2.1 Identification of substan ces relative to TG Ballastcleaner

Substance Chemical
Formula Identification no. Concentration

Active Substance: Sodium hypochlorite NaClO CAS no. 7681-52-9 EINECS no. 231-668-3 UN no. 1791 IMCO Class 8.0 5–13 wt% (as free available chlorine * )
*hereafter it is described as FAC Other Components: Sodium hydroxide NaOH CAS no. 1310-73-2 EINECS no.215-185-5 UN no. UN1824 IMCO Class 8.0 Less than 1 wt% in amount corresponding to 12% FAC

Sodium chloride NaCl CAS no. 7647-14-5 Less than 13 wt% in amount corresponding to 12% FAC
Relevant Chemicals: Hypochlorous acid HClO CAS no. 7790-92-3 ---
Chloroform CHCl 3 CAS no. 67-66-3 ---
Bromodichloromethane CHBrCl 2 CAS no. 75-27-4 ---
Dibromochloromethane CHBr 2 Cl CAS no. 124-48-1 ---
Bromoform CHBr 3 CAS no. 75-25-2 --- Hypobromous acid HBrO CAS no. 13517-11-8 --- Sodium hypobromite NaBrO CAS no. 13824-96-9 ---
Sodium bromate NaBrO 3 CAS no. 7789-38-0 ---
Monochloroacetic acid CH 2 ClCOOH CAS no. 79-11-8 ---
Dichloroacetic acid CHCl 2 COOH CAS no. 79-43-6 ---
Trichloroacetic acid CCl 3 COOH CAS no. 76-03-9 ---
Bromochloroacetic acid CHBrClCOOH CAS no. 5689-96-8 ---
Bromodichloroacetic acid CBrCl 2 COOH CAS no. 71133-14-7 ---

Dibromochloroacetic acid CBr 2 ClCOOH CAS no. 5278-95-5 ---

Bromoacetic acid CH 2 BrCOOH CAS no. 79-08-3 ---
Dibromoacetic acid CHBr 2 COOH CAS no. 631-64-1 ---
Tribromoacetic acid CBr 3 COOH CAS no. 75-96-7 ---
Chloroacetonitrile CH 2 ClCN CAS no. 107-14-2 ---
Dichloroacetonitrile CHCl 2 CN CAS no. 3018-12-0 ---
Trichloroacetonitrile CCl 3 CN CAS no. 545-06-2 ---
Dibromoacetonitrile CHBr 2 CN CAS no. 3252-43-5 ---
Bromochloroacetonitrile CHBrClCN CAS no. 83463-62-1 ---
Monochloramine NH 2 Cl CAS no. 10599-90-3 ---MEPC 57/2/8 ANNEX Page 8

I:\MEPC\57\2-8.doc Table 3.1.2.2 Identification of substances relative to TG Environmentalguard

Substance Chemical
Formula Identification no. Concentration

Active Substance: Sodium sulfite Na 2 SO 3 CAS no. 7757-83-7 More than 10 wt%

Other Component and
Relevant Chemical: Sodium sulfate Na 2 SO 4 CAS no. 7757-82-6 Less than 5 wt%

3.1.3 Chemical substances to be examined

Among chemical substances described in the previ ous section, the substances excluded from the examination and the reasons for exclusion are as follows:

.1 Concentration formed in the chemical reac tion is very low compared to the natural concentration in seawater, less than 1/500 and 1/100, respectively: NaCl, Na 2 SO 4
.2 To be reduced by added sodium sulf ite: NaClO, HClO, HBrO, NaBrO, NH 2 Cl

.3 To form salt and water after reacting with components in water. Not change pH of the ballast water: NaOH

.4 To become another chemical substance, sodium sulfate, rapidly: Na 2 SO 3
Consequently, chemical substances to be examin ed are sodium sulfite (acute toxicity only), sodium bromate, trihalomethanes, ha loacetic acids and haloacetonitriles.

3.2 Data set of “Active Substance”, “Other Components” and “Relevant Chemicals”

The toxicity of the selected fi ve chemical substances and groups , related with TG Ballastcleaner and TG Environmentalguard to aquatic organisms was examined using references such as IUCLID (International Uniform Chemical Information Database), OECD SIDS (Screening Information Data Sets) and EC OTOX (United States EPA Database).

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

Acute and chronic toxicity to aquatic organisms

Acute and Chronic Toxicity is shown in Tables 3.2.1.1 to 3.2.1.6.MEPC 57/2/8 ANNEX

Page 9

I:\MEPC\57\2-8.doc Table 3.2.1.1 Acute toxicity value of the mo st sensitive species to trihalomethanes

Substance Type/Organism Endpoint Concentration (mg/l) Reference

Fish (Freshwater) ( Lepomis macrochirus ) LC 50 96h 18 IUCLID

Fish (seawater) ( Limanda limanda) LC 50 96h 28 as above

Crustacean (Freshwater) (Daphnia magna) EC 50 48h 29 as above

Crustacean (seawater) Brine shrimp ( Artemia salina ) EC 50 24h 30.37 G.D. Foster et al. (1984)

Phytoplankton (Freshwater) ( Chlamydomonas reinhardtii ) EC 50 72h 13.3 IUCLID Chloroform

Aquatic Plant (seawater) Diatom ( Skeletonema costatum ) EC 50 120h 437 as above

Fish Common carp ( Cyprinus carpio ) egg EC 50 72-120h 67.4 J.S. Mattice et al. (1981)Bromodichloromethane

Crustacean Ciliate ( Tetrahymena pyriformis ) EC 50 24h 240 Y. Yoshioka et al. (1985)

Fish Common carp ( Cyprinus carpio ) egg LC 50 72- 120h 33.5 J.S. Mattice et al. (1981)Dibromochloromethane

Crustacean Ciliate ( Tetrahymena pyriformis ) EC 50 24h 65 Y. Yoshioka et al. (1985)

Fish (Freshwater) Bluegill ( Lepomis macrochirus ) LC 50 96h 29 R.J. Buccafusco et al. (1985)

Fish (Seawater) Sheepshead minnows ( Cyprinodon variegatus ) LC 50 96h 7.1 G.S. Ward et al. (1981)

Crustacean (Freshwater) Water flea ( Daphnia pulex ) LC 50 96h 44 J.R. Trabalka et al. (1977) Crustacean (Seawater) Brown Shrimp ( Peaneus aziecus ) LC 50 96h 26 ECOTOX

Phytoplankton (Freshwater) Green algae ( Selenastrum capriocornutum ) EC 50 96h 38.6 PAN Pesticides Database Bromoform

Phytoplankton (Seawater) Diatom ( Skeletonema costatum ) EC 50 96h 12.3 ECOTOX

From the above data, the acute toxi city values of the most sensit ive species to tr ihalomethanes, chloroform, bromodichloromethane, dibrom ochloromethane, and bromoform are 13.3, 67.4, 33.5 and 7.1 mg/l, respectively.MEPC 57/2/8 ANNEX Page 10

I:\MEPC\57\2-8.doc Table 3.2.1.2 Chronic toxicity value of the mo st sensitive species to trihalomethanes

Substance Type/Organism Endpoint Concentration (mg/l) Reference

Chloroform Fish ( Oncorhynchus mykiss ) LC 50 27d 2.03 IUCLID

Crustacean ( Daphnia magna ) NOEC 21d 13 as above

Phytoplankton Diatom ( Skeletonema costatum ) NOEC 5d 216 U.M. Cowgill et al. (1989)

Bromoform Fish Sheepshead minnow ( Cyprinodon variegatus ) NOEC 4d 2.9 P.T. Heitmuller et al. (1981)

Mollusk Littleneck clam ( Protothaca staminea ) Not reported 7 C.I. Gibson et al. (1979) NUREG/CR-0835 PNL-3023 Phytoplankton Green algae ( Selenastrum capricornutum ) NOEC 4d 10 Pan Pesticides Database

From the above data, the chronic toxicity values of the most sensitive species to chloroform and bromoform are 2.03 mg/l (LC 50 27d) and 2.9 mg/l (4d), respectivel y. Chronic toxicity data is not found for bromodichloromethane and dibromochloromethane.

Table 3.2.1.3 Acute toxicity value of the mo st sensitive species to sodium bromate

From the above data, the acute toxicity value of the most sensitive species to sodium bromate is > 30mg/l (EC 50 ). Type Organism Endpoint Concentration (mg/l) Reference

Mollusk Pacific oyster ( Crassostrea gigas ) EC 50 96h > 30 E.A. Crecelius (1979)
Nematodes & Flatworms Planarian ( Polycelis nigra ) LT 50 48h 3,018 J.R. Erichsen Jones (1941)MEPC 57/2/8 ANNEX Page 11

I:\MEPC\57\2-8.doc Table 3.2.1.4 Acute toxicity value of the most sensitive species to haloacetic acids and haloacetonitriles

Substance Type Organism Endpoint Concentration (mg/l) Reference

Rotifera (monochloroacetic acid) Rotifer ( Brachionus calyciforus ) EC 50 48h 68.9 P. Radix et al. (1999)

Phytoplankton algae (monochloroacetic

acid) Green algae ( Scenedesmus subspicatus ) EC 50 48h 0.028 R. Kuhn et al. (1990)

Others Amphibian (dichloroacetic acid) African clawed frog ( Xenopus laevis ) EC 50 96h 3,560 D.J. Fort et al. (1993)

Fish (trichloroacetic acid) Fathead minnow ( Pimephales promelas ) LC 50 96h 2,000 W.H. Dennis Jr. et al. (1979)

Others Amphibian (trichloroacetic acid) African clawed flog ( Xenopus laevis ) EC 50 96h 1,740 D.J. Fort et al. (1993)
Phytoplankton algae (trichloroacetic acid) Green algae ( Chlorella pyrenoidos a) LC 50 14d 0.3 T. Bednarz (1981)

Crustacean (bromoacetic acid) Water flea ( Daphnia magna ) EC 50 24h 65 R. Kuhn et al. (1989) Phytoplankton (bromoacetic acid) Green algae ( Scenedesmus subspicatus ) EC 50 72h 0.2 as above (1990)Haloacetic acids

Fish (dibromoacetic acid) Fathead minnow ( Pimephales promela s) LC 50 96h 69 M.A. Mayes et al . (1985) ECOTOX
Haloacetonitriles Fish (dibromoacetonitrile) Fathead minnow ( Pimephales promelas ) LC 50 96h 0.55 M.A. Mayes et al. (1985)

From the above data, the acute toxi city values of the most sensit ive species to ch loroacetic acid, dichloroacetic acids, trichloroacetic acid, bromoacetic acid and dibromoacetonitrile are 0.028, 3560, 0.3, 0.2 and 0.49 mg/l (LC 50 for dibromoacetonitrile and EC 50 for others), respectively. Acute toxicity data is not found for other chemical substances.

Table 3.2.1.5 Chronic toxicity value of the mo st sensitive species to haloacetic acids

Substance Type/Organism Endpoint Concentration (mg/l) Reference

Chloroacetic acid Crustacean Water flea ( Daphnia magna ) NOEC 21d 32 R. Kuhn et al. (1989)

Bromoacetic acid Crustacean Water flea ( Daphnia magna ) NOEC 21d 3.2 as above

From the above data, the chronic toxicity value of the most sensitive spec ies to chloroacetic acid and bromoacetic acid are 32 and 3.2mg/l (NOEC 21days ), respectively. Chronic toxicity data is not found for other ch emical substances.MEPC 57/2/8 ANNEX Page 12

I:\MEPC\57\2-8.doc Table 3.2.1.6 Acute toxicity values of the mo st sensitive species to Sodium sulfite

Type Organism Endpoint Concentration (mg/l) Reference

Fish Leuciscus idus NOEC 96h LC 50 96h 220 220-460 IUCLID

Crustacean Daphnia magna TL m 100h 203 as above

Mollusk Buccinum undatum LC 50 24h 400 as above

Echinoderm Psammechinus miliaris LC 50 24h 330(as SO 3 ) as above

Phytoplankton Green algae ( Chlamydomonas reinhardtii ) ( Chlorella vulgaris ) ( Scenedesmus basiliensis ) EC 50 8.9h EC 50 6.4h EC 50 8.2h 16-32 (as SO 3 ) as above as above as above

A. STAMM (1980)

From the above data, the acute to xicity value of the most sensit ive species to sodium sulfite is 25.2mg/l (EC 50 ) (16mg/l as the co ncentration of SO 3 ).

Because all the toxic data is more than NOEC 0.01 mg/l, all of these chemical substances are concluded as “not toxic.”

3.2.2 Endocrine disruption

On the “Active Substances”, the “Other Compon ents” and the “Relevant Chemicals” concerning TG Ballastcleaner and TG Environmentalguard, no endocrine disruption is listed in various databases such as EC list.

3.2.3 Sediment toxicity

Sediment toxicity is determined by using the absorption coefficient (K oc ) of soil. The representative “Relevant Chemicals” such as chloroform are obtained from ECOTOX. All the chemicals under evaluation have K oc values less than 500 l/kg. Thus the evaluation for the effects on benthic organisms is unnecessary.

3.2.4 Bioavailability / biomagnifi cation / bioconcentration

The log Pow (parameter for bioaccumulation) for any of the selected chemicals is less than 3, thus they cannot be judged to show great bioaccumulation tendency, and testing of them is unnecessary. BCF values are calcul ated by using the regression formula, log BCF = 0.767log P ow - 0.929. Results are shown in Table 3.2.4.1.MEPC 57/2/8 ANNEX Page 13

I:\MEPC\57\2-8.doc Table 3.2.4.1 Bioavailability / Biomagnification / Bioconcentration

Chemical substance logPow BCF (l/kg) Reference
Relevant Chemicals Chloroform 1.52 1.7 Syracuse Research Corporation, Bromodichloromethane 1.61 2.0 Syra cuse Research Corporation, Dibromochloromethane 1.70 2.4 Syra cuse Research Corporation, Bromoform 1.79 2.8 Syracuse Research Corporation,
Sodium bromate -7.18 3.7×10 -7 Syracuse Research Corporation,
Chloroacetic acid 0.34 2.1×10 -1 Syracuse Research Corporation,
Dichloroacetic acid 0.52 3.0×10 -1 Syracuse Research Corporation, Trichloroacetic acid 1.44 1.5 Syracuse Research Corporation,
Bromochloroacetic acid 0.61 3.5×10 -1 Syracuse Research Corporation,
Bromoacetic acid 0.43 2.5×10 -1 Syracuse Research Corporation,
Dibromoacetic acid 0.70 4.1×10 -1 Syracuse Research Corporation,
Chloroacetonitrile 0.11 1.4×10 -1 Syracuse Research Corporation,
Dichloroacetonitrile 0.29 2.0×10 -1 Syracuse Research Corporation, Trichloroacetonitrile 1.21 1.0 Syracuse Research Corporation,
Bromoacetonitrile 0.20 1.7×10 -1 Syracuse Research Corporation,
Dibromoacetonitrile 0.47 2.7×10 -1 Syracuse Research Corporation,
Monochloramine -1.19 1.4×10 -2 Syracuse Research Corporation,

Active substance
Sodium Sulfite -7.78 1.3×10 -7 Syracuse Research Corporation, Other component
Sodium sulfate -4.38 5.2×10 -5 Syracuse Research Corporation,

Because the BCF values obtained are less than 500 l/kg (wet weight), evaluation of crosscontamination (effects of concentrat ion and migration) is unnecessary.

Food web/population effect

For the reasons described above, there are no chemical substances applied to this category.

3.3 Data on mammalian toxicity

The mammalian toxicity of the “A ctive Substances” and the “Other Components” is evaluated by using the available data here. Chemical substances under evalua tion are listed in Table 3.3.1.

Table 3.3.1 “Active Substances” and “Other Components” for Mammalian toxicity

Product Substance Concentration TG Ballastcleaner Sodium hypochlorite 5–13 wt% (as FAC)
Sodium sulfite > 10 wt% TG Environmentalguard
Sodium sulfate < 5 wt%MEPC 57/2/8 ANNEX Page 14

I:\MEPC\57\2-8.doc The following two “Other Components” of TG Ballastcleaner shown in Table 3.1.2.1 are excluded:

Sodium hydroxide – one of general purpose ch emicals, which is evaluated as “non toxic” in OECD SIDS (2002).

Sodium chloride – a major constituent of seawater.

3.3.1 Acute toxicity

The most sensitive data for acu te toxicity are shown in Tabl e 3.3.2, and they are moderately toxic.

Table 3.3.2 Oral toxicity of ch emical substances to mammals

Substance Species (animal) LD 50 Reference Sodium hypochlorite Rat 1.23–1.46 g/kg ECBI/14/05

Sodium sulfite Rat 2.61 g/kg bw IUCLID, Na 2 SO 3, (2000)

Sodium sulfate Mouse 5.99 g/kg bw OECD SIDS, Okahara ,(2005)

3.3.2 Effects on skin and eye

The most sensitive data for effect on skin ir ritation are shown in Table 3.3.3. There are some irritation effects for sodium hypochlorite at eac h concentration, while no effects are found for sodium sulfite and sodium sulfate.

The most sensitive data for effect on eye ir ritation are shown in Table 3.3.4. There are some irritation for sodium hypochlorite and sodium sulf ate, but no effects are found for sodium sulfite.

Table 3.3.3 Effects on skin irritation

Substance Species (animal) Exposure duration Concentration Observation and remark Reference

Sodium hypochlorite Rabbit 6 24 hours 12.7% (as FAC) Intact skin and abraded skin Result: Moderately irritating ECBI/14/05, Colgate Palmolive,(1985)

Sodium sulfite Rabbit Not reported Not reported Not irritating
Draize IUCLID, Na 2 SO 3, (2000)

Sodium sulfate Rabbit 4 hours
Occlusive 500 mg Sligtly irritating
EC classification-not irritating OECD 404, Draize OECD SIDS, Na 2 SO 4, (2005)MEPC 57/2/8 ANNEX Page 15

I:\MEPC\57\2-8.doc Table 3.3.4 Effects on eye irritation

Substance Species (animal) Exposure duration & concentration Method Observation and remark Reference

Sodium hypochlorite Rabbit
6 14days
12.7% Draize method Severely irritating. Recovery not complete at 14days ECBI/14/05, Colgate Palmolive,(1985)
Sodium sulfite Rabbit Not reported BASF-test Not irritating IUCLID,
Na 2 SO 3, (2000)
Sodium sulfate Rabbit 90 mg, pulverized
into conjunctival

sac OECD guideline 405 Slight irritating redness of the conjunctiva observed. The redness was reversible within 7 days. OECD SIDS,
Na 2 SO 4, (2005)

From the data shown above, the conclusion is given as follows:

Sodium hypochlorite causes irritations on sk in and eye at each production concentration, but sodium sulfite has no effect. Sodium su lfate has only slight irritation. There are no data of skin sensitization for sodium hypochl orite at the production concentration and no data at all for sodium sulfite and sodium sulfate. OECD SIDS ( 2005 ) concluded that skin sensitization to sodium sulfate is highly unlikely.

3.3.3 Chronic and long-term toxicity

The most sensitive data for chr onic toxicity are shown in Tabl e 3.3.5. For sodium hypochlorite and sodium sulfite, no effects are observed fo r chronic and long-term toxicity. For sodium sulfate, OECD SIDS concluded that “Since this substance has no discernable systemic toxicity, a tentative chronic NOAEL that is equal to or great er than 320 mg/kg/day in rats would seem to provide a reasonable margin of safety.”MEPC 57/2/8 ANNEX Page 16

I:\MEPC\57\2-8.doc Table 3.3.5 Chronic toxicity of chemical substances to mammals

Substance Species (animal) Dosage route & concentration Duration of treatment Observation and remark Reference

Sodium hypochlorite B6C3F1
Mice Drinking water 0, 70, 140 and 275 mg/l as FAC 2 years Significant decrease in body weight at the highest dose was observed but it was ascribed to less water consumption. ECBI/14/05

Sodium sulfite No data. WHO has recognized as non toxic. WHO Food Additives Series21 IPCS INCHEM Home
Sodium sulfate Rats Sprague dawley In food 0.84% in diet 27 and 44 weeks daily NOAEL 320-400 mg/kg/day Mortality, tumor, Body weight, food and water consumption OECD SIDS, Na 2 SO 4, (2005)

3.3.4 Developmental and reproductive toxicity

The typical data for developmental toxicity are shown in Table 3.3.6, and there are no significant effects except sodium hypochlorite that has minor effects. The typical data obtained for reproductive toxicity are shown in Table 3.3.7. But no effect is found for these three chemical substances.

Table 3.3.6 Development toxicity of chemical substances to mammals

Substance Species (animal) Dosage route & concentration Duration of treatment Observation and remark Reference

Sodium hypochlorite Female SD rats Drinking water 0, 0.1, 1 and 10 mg/kg/day (mg FAC/kg/day) 2.5 months prior to conception and throughout gestation Minor effects at 100 mg/l ECBI/14/05

Sodium sulfite Rat Wistar Oral Feed 0.32; 0.63; 1.25; 2.5 and,5% (300, 1100, 2100 and 3300 mg/kg) 8-20 days of gestation, daily 20 days and after birth. No significant effect IUCLID Na 2 SO 3 (55)(56)(57)

Sodium sulfate The limited available data give no indication that sodium sulfate is toxic for development. OECD SIDS (2005)MEPC 57/2/8 ANNEX Page 17

I:\MEPC\57\2-8.doc Table 3.3.7 Reproductive toxicity of chemical substances to mammals

Substance Species (animal) Dosage route & concentration Duration of treatment Observation and remark Reference

Sodium hypochlorite LongEvans rats Gavage Males: 66 days Females: 35 days No effects observed ECBI/14/05

Sodium sulfite No data With WHO’s recognition testing for reproductive toxicity is deemed unnecessary. WHO Food Additives Series 21 IPCS INCHEM Home
Sodium sulfate The available data on fertility are quite limited but in view of the fact that the substance is abundantly oc curring in the body, toxicity for reproduction is unlikely. OECD SIDS (2005)

3.3.5 Carcinogenicity and mutagenicity

The typical data for carcinogenic ity are shown in Table 3.3.8, and th ere are no significant effects.

The typical data for mutagenic ity are shown in Table 3.3.9. Alt hough in vitro test some results are positive for sodium hypochlorite, in vivo test results show negative. There are no in vivo test results available for sodium sulfite and sodium su lfate, but in vitro test results are negative.

Table 3.3.8 Carcinogenicity of ch emical substances to mammals

Substance Species (animal) Type of test, duration Doses (mg/l, FAC) Observation and remark Reference

Sodium hypochlorite Rat Oral, drinking water, 104 weeks Males: 0, 475 and 950 Females: 0, 950 and 1,900 Negative ECBI/14/05

Sodium sulfite No specific data IARC designates as “group 3”. Pan Pesticides Database
Sodium sulfate Swiss albino mice Carcinogenicity 26 weeks, daily 31 μg in 0.01 ml (0.9%) per g body weight, s.c. injected Tumor of subcutis and/or skin in 1% of the female and 4% in male (normal for this strain in this lab). OECD SIDS (2005)MEPC 57/2/8 ANNEX Page 18

I:\MEPC\57\2-8.doc Table 3.3.9 Mutagenicity of chemical substances to mammals

Substance Species Type of test Concentration (mg/l) Observation and remark Reference

Sodium hypochlorite In vivo : mouse BM Micronucleus 312.5–2,500 mg/kg Negative ECBI/14/05

Sodium sulfite In vitro : Salmonella typhimurium OECD Guide-line 471 “Genetic Toxicology: Salmonella typhimurium Reverse Mutation Assay” 20-500 μg/ plate Metabolic activation: with and without Negative IUCLID Na 2 SO 3 (2000)

Sodium sulfate In vitro : Salmonela typhimurium Ames test under GLP
Salmonella Microsome test 312-5,000μg Metabolic S-9 activation: with and without Negative OECD SIDS (2005)

From the above data sodium hypochlorite, major component of TG Ballastcleaner, and sodium sulfate, the “Other Components” of TG Environmentalguard, s how slight acute and chronic toxicity, and irritation to skin and eye. Except vents of storage tank, these chemicals are treated within closed piping system where they are supplie d from storage tank to ballast line. Therefore, there is no possibility of crew’ exposure to thes e chemicals during the ordinary ballasting and deballasting operations.

On the other hand, there are po ssibilities that crew are expos ed to these chemicals during operation of filling up to storage tanks and flushi ng of leaked chemicals from tanks or piping. During these operations it is necessary for crew to work with sufficient protections based on the operation manuals. Instructions on these sp ecial works are described in chapter 5.

3.4 Physical and chemical properties of the “Active Substances” and the treated ballast water

The physical and chemical properties of the “Ac tive Substances” and the “Other Components” of TG Ballastcleaner are investigated. Those of sodium sulfite, the “A ctive Substance” of TG Environmentalguard and sodium sulfate, the “Other Component” and the “Relevant Chemicals” of TG Environmentalguard, are also investigated. The data for ”Relevant Chemicals” are not listed in this summary.

Tables 3.4.1 and 3.4.2 show the physical and chemical propertie s of TG Ballastcleaner and TG Environmentalguard.MEPC 57/2/8 ANNEX Page 19

I:\MEPC\57\2-8.doc Table 3.4.1 Physical and chemical properties of TG Ballastcleaner

Classification Active Substance Other Component Other Component

Trade name TG Ballastcleaner

Chemical name Sodium hypochlorite Sodium hydroxide Sodium chloride Molar mass 74.44 g/mol 40.00 g/mol 58.44 g/mol

Formula NaClO NaOH NaCl
Melting point -20 to -30oC 323oC 801oC
Boiling point 96 to 120oC at 1013 hPa 1388oC 1413oC Specific gravity 1.15 (13.1wt% as FAC) aqueous solution at 25oC 1.00 (0.04wt%)
at 27oC 1.10 (3 wt%) at 23oC

Vapor Pressure 17.4 – 20 kPa at 20oC 0.133 kPa at 739oC 0.133 kPa at 865oC
Aqueous solubility 29.3 g/100g at 0oC 109 g/100 g at 20oC 35.6 g/100 g at 0oC

PH >11.5 12 in 0.05 wt% Neutral

Octanol-water partition coefficient logPow=-3.42 logPow=-3.88 logPow=-0.46

Table 3.4.2 Physical and chemical pr operties of TG Environmentalguard

Classification Active Substance Other Component Trade name TG Environmentalguard

Chemical name Sodium sulfite Sodium sulfate

Molar mass 126.04 g/mol 142.05 g/mol

Formula Na 2 SO 3 Na 2 SO 4 Melting point 600oC 888oC
Boiling point None (To become sodium sulfate) 1429 oC Specific gravity 1.10 g/cm3 (11wt%) at 23oC 1.10 g/cm3 (10wt%) at 27oC
Vapor Pressure Substantially 0 mm Hg at ambient temperature Substantially 0 mm Hg at ambient temperature Aqueous solubility 13.8 g/100g at 0oC 19.5 g/100g at 0oC

PH > 10 Neutral
Octanol-water partition coefficient logPow=-7.8 logPow=-4.4MEPC 57/2/8 ANNEX Page 20

I:\MEPC\57\2-8.doc 4 RISK ASSESSMENTS

Risk assessments for chemical substance concerni ng the chemical behavior within ballast water were undertaken before screening of persistency (P), bioaccumulation (B) and toxicity (T) are evaluated.

4.1 Reactions of TG Ballastcleaner (Sod ium Hypochlorite) in ballast water

Sodium hypochlorite, the main i ngredient of TG Ballastcleaner, is chemically changed into hypochlorite, hypobromite, sodium hypobromous acid and chloramine in the ballast water.

4.2 Reactions of TG Environmentalguard (Sodium Sulfite) in ballast water

Sodium sulfite, the main ingredient of TG Envi ronmentalguard, reduces residual chlorine by the following reaction:

NaClO + Na 2 SO 3 NaCl + Na 2 SO 4 The excess of sodium sulfite becomes sodium sulfate by reacting with dissolved oxygen in ballast water by the following reaction:

2Na 2 SO 3 + O 2 2 Na 2 SO 4 This reaction temporarily decreases the disso lved oxygen concentration in water where the ballast water treated with TG Environmentalguard is discharged. But the treated ballast water is discharged into surface layer water, which is in equilibrium with the atmosphere and even large amount of TG Environmentalguard is unlikely to adversely affect the environment because the natural concentration of disso lved oxygen is quickly supplied from atmospheric oxygen.

4.3 Selection of chemical substances for presenting risks to environment

The chemical substances to be evaluated here ar e sodium sulfite (acute toxicity only), sodium bromate, trihalomethanes, haloacetic acids and haloacetonitriles as described in Section 3.1.3.

4.4 Exposure assessment on aquatic organisms

Five chemical substances and groups select ed above are evaluate d based on PBT criteria.

4.4.1 Persistence test (P)

From the data gathered, some organic chem icals undergo reductive decomposition in the anaerobic environment of sediment. As the enviro nment under consideration is the treated ballast water and surrounding water where it is discha rged, trihalomethanes, haloacetic acids, haloacetonitriles and sodium bromate are determ ined as persistent in accordance with PBT criterion for persistency (half-lif e periods in hydrolysis is greater than 60 days in seawater).MEPC 57/2/8 ANNEX Page 21

I:\MEPC\57\2-8.doc 4.4.2 Bioaccumulation test (B)

No observed data for inorganic chemicals is available, but inorganic chemicals and their “Relevant Chemicals” are not thought to be bioaccumulate because they are water-soluble.

The log Pow, the bioavailability / biomagnification / bioaccumulation factor is smaller than 3 for all substances. Therefore, they are thought unlikely to be bioaccumulative and do not require testing. The log BCF values are obtained using the regression formula, log BCF = 0.767log Pow - 0.929 (R 2 =0.793, n=199, 95% confid ence interval: ±1.027) substituting log Pow values to this equation.

Because obtained BCF values in Table 3.2.4.1 are far less than 500 l/kg, evaluation of cross-contamination (effects of concentration) is unnecessary.

4.4.3 Toxicity test of substances (T)

Because all the chronic toxicity values (NOEC) shown in Tables 3.2.1.1 to 3.2.1.6 are greater than 0.01mg/l, no toxic substance is judged to ex ist among to the chemical substances to be evaluated.

4.4.4 Evaluations based on PBT criteria

Based on the results described abov e, PBT criteria are identified for each chemical substance in consideration. Results are shown in Table 4.4.1.

Table 4.4.1 PBT Criteria on trihalomethanes, sodium bromate, haloacetic acids, haloacetonitriles and sodium sulfite

Substance for PBT criteria Persistence (P) ( Yes or No ) Bioaccumulation (B) ( Yes or No ) Toxicity (T) ( Yes or No )

Trihalomethanes Yes No No
Sodium bromate Yes No No
Haloacetic acids Yes No No
Haloacetonitoriles Yes No No
Sodium sulfite No No No

Because there are no substances which meets P, B and T all together, all substances under investigation are designated as non-PBT materi al. The effects on aquatic organisms of above substances are to be evaluated using the following toxic tests and PEC/PNEC values.

4.5 Evaluation for effect of treated ballast water to aquatic organisms

The simulated ballast water is defined as follows:

.1 Test water is filtered to remove large aquatic organisms and particles, and then disinfected with TG Ballastcleaner at a FAC concentration of 30 mg/l;MEPC 57/2/8 ANNEX Page 22

I:\MEPC\57\2-8.doc .2 Residual chlorine in test water is reduced and eliminated by adding TG Environmentalguard after five days storage under dark condition; and

.3 Added TG Environmentalguard is 0.021% of testing water in weight corresponding to a sodium su lfite concentration of 22 mg /l when the concentration of sodium sulfite in TG Environmentalguard is 10%.

Initial injection quantity of TG Ballastcleaner ca n be decreased by using this injection control system in reference to the resi dual chlorine co ncentration immediately af ter injection. This is based on the fact that initial decrease of residual chlorine is affected by water quality pumped up into ballast tank. Consequently adding quantity of TG Ballastcleaner and TG Environmentalguard can be decreased and this leads to the d ecrease of by-products.

4.5.1 Toxic testing of the simulated ballast water

The toxic tests were carried out und er OECD guidelines, and the deta il is described in a separate document. In these tests three t ypes of organism were exposed to the simulated ballast water at two different levels of dosages in a way that simulated the treatment of ballast water. The dosages of TG Ballastcleaner were 0.016% a nd 0.024% of seawater, those are equivalent to FAC concentrations of 20 mg/l and 30 mg/l. Tested organisms were Java medaka on fish, marine Gammarid Hyale barbicornis on crustacean and Skeletonema costatum on algae (diatom).

These results suggest that the simu lated ballast water at both dosage levels do not have lethal or sublethal effects on the first two organisms, Java medaka and marine Gammarid, in the early life stages

. However, the results indicate that the diatom Skeletonema costatum is slightly affected by the seawater at both dosage levels. There are no serious acute toxic effects, but there are statistically differences in the growth rate, thos e are slightly lower than that of the controlled group, at both dosage levels.

The results of experiments using dilutions of the 0.024% solution show that regardless of the degree of dilution (1/2.29, 1/5.24, 1/12, or 1/27.5) an in crease in cellular de nsity is seen. A dilution required to observ e a effect of LOEC was 1/ 2.29, and that of NOEC was 1/5.24.

These results indicate that organisms in the water into which the treated ballast water is discharged will not be affected at all wh en the ballast water is diluted to 1/5.24.

4.5.2 Environmental effect tests

Concentrations of the evaluated five chemical substances and groups in the simulated ballast water were measured for both seawater and fr eshwater. The results are shown in Table 4.5.1 together with acute toxicity valu es collected in sections 3.2.1 and 3.2.4.MEPC 57/2/8 ANNEX Page 23

I:\MEPC\57\2-8.doc Table 4.5.1 Measured concentrations of halo acetic acids and ha loacetonitriles in simulated ballast water (haloacetic acids and haloacetonitriles)

Chemical substance Conc. in simulated ballast water (mg/l) Acute toxicity value (mg/l) Chronic toxicity value (mg/l)

monochloroacetic acid 0.002 0.028 32 Dichloroacetic acid 0.022 3,560 No data
Trichloroacetic acid 0.03 0.3 No data
Bromochloroacetic acid 0.003 No data No data
Bromodichloroacetic acid <0.01 No data No data
Dibromochloroacetic acid <0.03 No data No data
Bromoacetic acid 0.007 0.2 3.2
Dibromoacetic acid 0.055 69 No data
Tribromoacetic acid <0.05 No data No data
Chloroacetonitrile <0.001 No data No data
Dichloroacetonitrile <0.004 No data No data
Trichloroacetonitrile <0.001 No data No data
Dibromoacetonitrile <0.001 0.49 No data
Bromochloroacetonitrile <0.001 No data No data

4.6 Model taking dilution into account

The degrees of dilution of these six chemical su bstances in harbours were evaluated by using the dilution calculation of the MA M-PEC model. The MAM-PEC mode l was developed in order to predict the concentrations of an tifouling agents painted on ship hulls in a harbour to prevent pollution of the marine environment.

The simulation results for these six chemical subs tances are obtained in the ballast water model in the Port of Rotterdam model. The obtained dilution factors for each chemical substance are shown in Table 4.6.1. Because sodium sulfite becomes sodium sulfate by a reaction with dissolved oxygen in the order of ten minutes, high degradation rate accounts for very small dilution factor.

Table 4.6.1 Dilution factors of chem ical substances to be assessed

Chemical substance Dilution factor
Chloroform 1/58
Bromoform 1/145
Monochloroacetic acid 1/252
Trichloroacetic acid 1/102
Bromoacetic acid 1/58
Sodium sulfite 1/67,600MEPC 57/2/8 ANNEX Page 24

I:\MEPC\57\2-8.doc 4.7. Evaluation using PEC/PNEC

PNEC values obtained by dividing acute toxicity values with assessment factors are shown in Table 4.7.1. These acute toxicity values are li sted in section 3.2.1. Assessment factor 100 is selected for sodium sulfite, as it has no rema ining characteristics. As sessment factor 1000 is selected for other chemical substances.

Table 4.7.1 Toxicity value and PNEC of chemical substances to be assessed

Toxicity Value Chemical substance Endpoint Concentration (mg/l) Assessment factor PNEC (μg/l)
Chloroform (freshwater) EC 50 72h 13.3 1000 13.3 Chloroform (seawater) LC 50 96h 28 1000 28 Bromoform (freshwater) LC 50 96h 29 1000 29 Bromoform (seawater) LC 50 96h 7.1 1000 7.1 Monochloroacetic acid EC 50 48h 0.028 1000 0.028 Trichloroacetic acid EC 50 96h 0.3 1000 0.3 Bromoacetic acid EC 50 72h 0.2 1000 0.2

Sodium sulfite EC 50 6.4- 8.9h 25.2 100 252

PEC/PNEC values are shown in Table 4.7.2. PEC values are calculated using MAM-PEC model in the Port of Rotterdam.

Table 4.7.2 PEC/PNEC of chemical substances to be assessed

Chemical substance Conc. in simulated ballast water (μg/l) Dilution factor PEC (μg/l) PNEC (μg/l) PEC/PNEC

Chloroform (freshwater) 40 1/58 0.69 13.3 0.052
Chloroform (seawater) 40 1/58 0.69 28 0.025
Bromoform (freshwater) 470 1/145 3.24 29 0.11
Bromoform (seawater) 470 1/145 3.24 7.1 0.46
Monochloroacetic acid 2 1/252 0.008 0.028 0.28
Trichloroacetic acid 30 1/102 0. 294 0.3 0.98
Bromoacetic acid 7 1/58 0.121 0.2 0.61
Sodium sulfite 22,000* 1/67,600 0.33 252 0.0013 (short)

* Calculated maximum concentration

For the excluded chemical substances, PEC/PNEC va lues are calculated as a reference using the dilution factor of 1/58, which is the most conservative value.MEPC 57/2/8 ANNEX Page 25

I:\MEPC\57\2-8.doc Table 4.7.3 PEC/PNEC of chemical substances to be assessed

Chemical substance Measured conc. (μg/l) Dilution factor PEC (μg/l) PNEC (μg/l) PEC/PNEC

Sodium bromate 9.4* 1/58 0.16 30 0.005

Bromodichloromethane 15 1/58 0.26 67.4 0.004

Dibromochloromethane 12 1/58 0.21 33.5 0.006

Dichloroacetic acid 22 1/58 0.38 3560 0.0001

Dibromoacetic acid 55 1/58 0.95 69 0.014 *Bromic acid concentration of 8μg/l is converted to sodium bromate concentration by multiplying by 151/128.

All the above chemical substances are confir med not to give adverse effects on aquatic environment because each PEC/PNEC value is less than one.

4.8 Evaluation of environmental exposure

Accordingly, dilution test of the above simula ted ballast water was conducted to determine the dilution factor with whic h the chronic toxicity to phytoplankton is negligible. The results showed that the LOEC and the NOEC (both described in dilution factor) we re obtained when the solutions are diluted 2.29 times and 5.24 times, re spectively. Therefore, no adverse effect will be expected.

The evaluation of environmental exposure is done for chemical substances contained in the treated ballast water discharge. The results sh ow that PEC/PNEC’s of examined 11 chemical substances are less than 1, and therefore, thes e values assure that th e treated ballast water discharge with TG Ballastclean er and TG Environmentalguard has no adverse effect on aquatic environment.

4.9 Assessment of exposure to humans

Possibility of exposures to humans

Because the ballast water management system is supposed to be controlled remotely and the all liquids listed above are flowing in a closed system, there is no possibility for humans to contact with those liquids in normal ope ration. For instance system configuration is shown in Fig. 4.9.1.

However, human’s exposure to those liquids can be assumed in the following cases:

.1 entering ballast tanks;

.2 leakage during filling operation of the chemicals;

.3 leakage of the chemicals from tanks, pumps valves and fittings on piping; and

.4 cleaning operation of chemicals leakage of .2 and .3.MEPC 57/2/8 ANNEX Page 26

I:\MEPC\57\2-8.doc During the above operations the work should be done wearing the appropriate protection devices as described in sections 5.3.1 and 5.3.2.

Fig. 4.9.1 System configuration

5 EFFECTS AND SAFETY OF SHIP AND CREW

5.1 Effects on ship’s hull

5.1.1 Effects on ballast tanks by TG Ballastcleaner

Although TG Ballastcleaner (sodium hypochlorite ) is corrosive, low residual chlorine concentration in ballast water with a pH around neutral, allows epoxy or plastic paint for the internal surface coating of ballast tanks. This coating should be done for ships without painting ballast tanks.

5.1.2 Effects on ballast tanks by TG Environmentalguard

TG Environmentalguard (sodium sulfite) as reductant has no other effect on ship.

5.1.3 Effects on outer hull

When the treated ballast water is discharged, it c ontains sodium sulfite. S odium sulfite works as a reducing agent and gets its str ong reducing power from transition metals such as iron and zinc. Therefore, it has no effects on the outer hulls of ship. Ballast water Filtration Water quality check

Ballast tank Departure

Voyage

Ballast tank Check of residual chlorine

Port entry

TG Environmentalguard Pum p Surrounding water TG Ballastcleaner

BALLASTING

DEBALLASTINGMEPC 57/2/8 ANNEX Page 27

I:\MEPC\57\2-8.doc 5.2 Ballast water treatment equipment

5.2.1 Outline of distribution system

TG Ballastcleaner and TG Environmentalguard ar e supplied from storage tanks to ballast line. The injections of the chemicals should be controlle d using remote control. Therefore, crew will never contact with these chemicals in normal wo rk to inject chemicals into ballast lines.

5.2.2 Materials of chemical storage tanks, pipes, and fittings

Materials used on board storage ta nks, piping and valves should be compliant with things which has been high performance in chemical manufacture s. Steel lined or coat ed with polypropylene, polyethylene, polyvinylchloride or titanium are suitable materials for TG Ballastcleaner tank. Above stated materials are also suitable for TG Ballastcleaner supplying a nd injection lines from storage tank into ballast lines. Also, corrosion re sistant materials should be used for chemical distribution pipes and valves of the system. Steel lined or coated with polypropylene or, polyethylene, and stainless steel, etc. are suita ble materials for TG Environmentalguard tank. Above stated materials are also suitable for TG Environmentalguard supplying and injection lines from storage tank into ballast lines and valves.

5.2.3 Storage of chemicals

The chemicals are supplied to storage ta nks of ships during berthing at ports.

5.2.4 Management of chemicals

TG Ballastcleaner should be kept below 20oC to prevent its decomposition and above 0oC to keep it away from freezing. TG Environmentalguard should be kept above 0oC to avoid freezing.

5.3 Crew safety and emergency responses

If the ballast water disinfectant system is run in a normal manner and maintained appropriately, it poses no threat to the safety or the crew. When TG Ballastcleaner and TG Environmentalguard are supplied from land to storage tanks onboard at port, the work should be done following the instruction in section 4.9.

In case of emergencies during the ballast water treatment system is in operation, chemical injection operation should be shut down by remote control syst em. In case of power failure, whole ballast water treatment system should be stopped and chemical injection valves are also automatically closed.

5.3.1 Leakage of TG Ballastcleaner

TG Ballastcleaner should be washed away with water after being reduced with TG Environmentalguard. Do not wipe it up with paper. Paper reacts w ith sodium hypochlorite, and heat is generated.

When handling leaked TG Ballastcleaner, the cr ew must wear protective goggles, masks, alkaline-resistant and chlorine-r esistant gloves, boots and helmet. Full apron or smock (made of chlorine-resistant fibers) is recommended. If sp lashing occurs, it should be immediately flushed away with a lot of water.MEPC 57/2/8 ANNEX Page 28

I:\MEPC\57\2-8.doc 5.3.2 Leakage TG Environmentalguard

Leaked small amount of TG Environmentalguard s hould be washed away with water or wiped up with cotton dust clothes. Even if the quantity of TG Environmen talguard is not small, it is sufficiently safe to be washed aw ay with large amount of water.

When handling leaked TG Environmentalguar d, crew must wear pr otective goggles, alkaline-resistant gloves, boots a nd helmet. As sodium sulfite doe s not react eas ily with other substances except oxidizer, TG Environmentalguard does no harm to crew. If splashing occurs, it should be immediately flushed away with wate r and wash the splashed spot with soap.

6 CONCLUSION

The “Active Substances”, the “Other Compon ents” and the “Relevant Chemicals” in the TG Ballastcleaner and TG Environm entalguard system used to treat ballast water are evaluated in terms of environmental effect according to Proce dure (G9). The results showed that the treated ballast water out of this chemical system does not have any adverse effects on the water into which it is discharged.

This chemical system is also deemed sufficiently safe to ships and crew, because the sufficient considerations are made on th e safety of ships and crew.MEPC 57/2/8 ANNEX Page 29

I:\MEPC\57\2-8.doc References

A.Stamm (1980), Der Einfuss von, “Sul fit auf das Wachstum und die CO 2 -Fixieung Einzellinger Grunalgen” Environmental Poll ution (Series A) 22, 91-99.

A.M. Beeton, P.K. Kovaci and A.S.Brooks (1976) , “Effects of chlorine and sulfite reduction on lake Michigan invertebrate s” EPA-600 13-76-036, PB-253-121.

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