I:\MEPC\57\2-2.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 57/2/2 7 September 2007 Original: ENGLISH

HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Basic Approval of Active Substances used by Hitachi Ballast Water Purification System (ClearBallast)

Submitted by Japan

SUMMARY

Executive summary: This document contains an applicat ion for Basic Approval of Active Substances used by Hitachi Ba llast Water Purification System (ClearBallast) in accordance with th e Procedure for approval of ballast water management systems that make use of Active Substance (G9) adopted by resolution MEPC.126(53) . Relevant documents and the complete dossier have been provide d to Marine Environment Division of the Organization for review by the GESAMP-Ballast Water Working Group.

Action to be taken: Paragraph 5

Related documents: BWM/CON/36; MEPC 56/2/2; and BWM.2/Circ.10

Introduction

1 The Ballast Water Management Convention (BWM Convention), in its regulation D-3.2, provides that ballast water management system s which make use of Active Substances, to comply with the Convention, shall be approve d by IMO based on a procedure developed by the Organization.

2 MEPC 53 adopted, by resolution MEPC.126(53), the ëProcedure for approval of ballast water management systems that make use of Activ e Substances (G9)í. Sec tion 8 of the Procedure 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 Administrations and repo rt to the Organization on its findings.

3 This document contains an application for Basic Approval of Active Substances used by Hitachi Ballast Water Purification System (Clear Ballast) in accordance with the Procedure (G9) and its annex provides the non-conf idential information on that syst em. Relevant documents and the complete dossier have been submitted to Marine Environment Division of the Organization for review by the GESAMP-B allast Water Working Group.MEPC 57/2/2 - 2 -

I:\MEPC\57\2-2.doc 4 The Hitachi Ballast Water Purification Sy stem (ClearBallast) holds excellence in treatment capability and is safe not only to ships and crew but also to the environment.

Action requested of the Committee

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

***MEPC 57/2/2

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

INFORMATION FOR BASIC APPROVAL OF ACTIVE SUBSTANCES USED BY

HITACHI BALLAST WATER PURIFICA TION SYSTEM (CLEARBALLAST)

This report is structured in accordance with th e headlines in the ìProcedure for approval of ballast water management systems that make use of Active Substances (G9)î.

1 INTRODUCTION

The purpose of this document is to clarify ma nagement responsibilities to the authorities concerned by providing data. Furthermore, th e document describes Hitachi Ballast Water Purification System and its impact on the enviro nment. This system uses coagulation magnetic separation as the major purification method in accordance with the Procedure (G9).

1.1 Glossary

Chemical Injector : A device to inject chemicals (triiron tetraoxide, PAC, or PASA), which is a part of the Hitachi Ballast Water Purification System.

Coagulator : A device to transform chemicals into fl ocs containing SS, pl ankton, bacteria, and so on, which is a part of the Hitach i Ballast Water Purification System.

Filter Separator : A device which removes flocs from the ballast water using a rotating filter drum, as a part of the Hitachi Ballast Water Purification System.

Floc : Gelatinous matter made up of fine partic les such as a suspension colloid in water (suspended solids) formed by an inorganic coagulant or high-polymer coagulant.

Inorganic Coagulant : A chemical containing metallic ions of aluminium or iron that forms a larger floc of fine particles dispersed in wate r such as a suspension colloid by neutralizing the charge on their surfaces.

Magnetic Disk : A component of the magn etic separator of this system. A disk in which magnets (permanent magnets) are embedded.

Magnetic Disk Array : A component of the magnetic separa tor of this system. An assembly consisting of several magnetic disks arranged coaxially.

Magnetic Separator : A device which removes flocs from the ballast water using a magnetic disk array, as a part of the Hitachi Ballast Water Purification System.

PAC (Poly Aluminium Chloride) : An inorganic coagulant consisting of poly aluminium chloride and referring to basic aluminium chloride.

PASA (Poly Acrylamide Sodium Acrylate) : A crosslinking chemical consisting of high molecular weight polymer particles with a negati vely charged surface, wh ich forms a coagulation of fine particles suspended in water such as a suspension colloid. It is a kind of Anionic High-Polymer Coagulant.MEPC 57/2/2

ANNEX Page 2

I:\MEPC\57\2-2.doc Rotating Filter Drum : A component of the filter separator of this system. A drum with metallic or plastic filters attached on the cylindrical frame and th at is continuously rotating.

Sludge Tank : Tank for storing the removed flocs contai ning chemicals, SS, plankton, bacteria, and so on, which is a part of the Hita chi Ballast Water Purification System.

SS (Suspended Solids) : Particulate substances in water th at are insoluble to water such as a suspension colloid. One of the indices that e xpresses the extent of suspension in water.

SS Concentration : Weight of suspended solids contained in 1 L of water in the unit of mg/L.

1.2 Features of Hitachi Ballas t Water Purification System

The Hitachi Ballast Water Purification System pu rifies water by removing target organisms and other objects using flocculating agents. The system effectively promotes collision between these small target organisms and aggregates to fo rm flocs, and separates the floc by magnetic separation technology to purify ballast water. The photograph shown in Figure 1-1 is of a pilot-scale test set-up of this system. Even when th e seawater intake is turbid with SS, this system efficiently removes such suspension components as well as bacteria and plankton so that transparent, clear treated ballast water is obtained.

Figure 1-1: Example of Hitachi Ballast Water Purification System

2 OUTLINE OF HITACHI BALLAST WATER PURIFICATION SYSTEM

2.1 Principle of purification of the system

This system employs a coagulation magnetic se paration method, in which organisms and other target objects are coagulated using coagulants and separate d by magnetic separation technology. Specifically, coagulants and triiron tetraoxide are added to the seawater to form small agglomerates of about 1 mm in diameter calle d flocs, containing plankton, bacteria and sand (Figure 2-1).MEPC 57/2/2

ANNEX

Page 3

I:\MEPC\57\2-2.doc Figure 2-2 shows the ballast water purification proce ss in this system. First, triiron tetraoxide is added to seawater containing plan kton, bacteria, and SS. Next, PA C and PASA are added to form
flocs. These flocs are then se parated from the seawater using permanent magnets. Finally, any flocs that were not removed by the magnetic separation are removed by filtering to produce purified water.

This coagulation magnetic separation method re moves not only plankton a nd bacteria but also sand, mud, and SS contained in the ballast water, th ereby reducing mud deposits (including muddy sediment such as dead organi sms) and alleviating m ud removal during ship inspections. With this system, the ballast water can be purified either during storage in the ballast tank, during intake, or during discharge. Purificati on during intake is the most effective way to ensure that a minimal amount of organisms an d SS enter the ballast tanks and thus reduces sediment build-up in the tanks. Therefore, most of our attention is focused on the system components and operations for purification during intake.

PAC and PASA are widely used in drinking wate r purification plants so the safety of these
chemicals has been confirmed. Triiron tetraoxide, whose composition is Fe 3 O 4 , is a natural resource that exists broadly in nature, as is generally known. Tabl e 2-1 shows the rated
concentration of each chemical used in th e coagulation magnetic separation method.

PAC and PASA

Triiron tetraoxide Plankton Bacteria

Figure 2-1: Schematic structure of a floc

Table 2-1: Rated concentration of each ch emical

Additive agent Additive concentration (mg/L)
Triiron tetraoxide 30 PAC 5 (as Al)

PASA 1MEPC 57/2/2

ANNEX Page 4

I:\MEPC\57\2-2.doc Figure 2-2: Outline of process of Hit achi Ballast Water Purification System

2.2 Specifications of the system

This section describes the specifications of the major components of the Hitachi Ballast Water Purification System described in the preceding sec tion. Figure 2-3 is a schematic diagram of the
structure of the Hitachi Balla st Water Purification System.

Since the Hitachi Ballast Water Purification System is automated, no manual operation by the crew is required and no dedicated operators for the purification system are necessary. Some manual operation is required for the pouring chemicals into the storage tank, preparing for unloading the sludge, and unloa ding the sludge onto land.

Coagulator Coagulator

Separation of floc containing Separation of floc containing triiron tetraoxide tetraoxide Formation and growth Formation and growth of floc containing of floc containing triiron tetraoxide tetraoxide Mixing chemicals, Mixing chemicals,

formation of formation of micro floc micro floc Filter separator separator

Retention time Retention time

- 0.5 min

0.5 min Flash mixer Flash mixer

Separating time Separating time

< 10 sec < 10 sec Magnetic Magnetic separator separator

Retention time Retention time

- 2 min Flocculation reactor Flocculation reactor Coagulator Coagulator

Separation of floc containing Separation of floc containing triiron tetraoxide tetraoxide Formation and growth Formation and growth of floc containing of floc containing triiron tetraoxide tetraoxide Mixing chemicals, Mixing chemicals,

formation of formation of micro floc micro floc Filter separator separator

Retention time Retention time

- 0.5 min

0.5 min Flash mixer Flash mixer

Separating time Separating time

< 10 sec < 10 sec Magnetic Magnetic separator separator

Retention time Retention time

- 2 min Flocculation reactor Flocculation reactor

Ballast Ballast

tank Triiron tetraoxide PAC

Seawater Seawater PASA Magnetic disk array

Injection Injection Injection Injection Rotating filter drum

Filter washing spray

Figure 2-3: Schematic diagr am of structure of Hitachi Ballast Water Purification System Seawater Ballast

pump Magnetic separator PASA Chemical injectors

Filter separator Ballast tank P Filter washing water

Residue from filter

Filter residue tank P Sludge

Sludge tank Flash
mixer Flocculation

reactor Triiron
tetraoxide
&
PAC Chemical injector

CoagulatorMEPC 57/2/2

ANNEX

Page 5

I:\MEPC\57\2-2.doc 2.2.1 Preparation for operation

Since some manual operation is required for the preparation of the purif ication operation, this section outlines the manual operation for the preparation.

Seawater PAC injector

Flash mixer Storage tank

P P M Fresh water Triiron tetraoxide injector

Storage tank
with auto-feeder Slurry mixer M:Mixer motor P:Pump

Injection pump

Injection pump

Flash mixer Flocculation reactor PASA solution injector

P Solution mixer Fresh water M Storage tank
with auto-feeder

Injection pump M:Mixer motor P:Pump

Figure 2-4: Schematic diagr ams of chemical injectors

2.2.2 Chemical injector

Each chemical injector has a liq uid or powder chemical storage ta nk, a slurry mixer or solution mixer, and a liquid chem ical injection pump.

Triiron tetraoxide and PASA are available on the market in powder form while PAC is available in liquid form. The two powder chemicals are convert ed into slurry or solution before injection by mixing them with fresh water on the ship. The three chemicals in liquid form are injected into the ballast water feed pipes through the injection pumps (Figures 2-2 and 2-3).

2.2.3 Coagulator

The coagulator consists of two types of mechan ical reactors: a flash mixer and a flocculation reactor (see Figure 2-3). The triir on tetraoxide and PAC injected fr om the chemical injectors are uniformly mixed in the flash mixer at high speed. In the process of sending the micro flocs from the flash mixer to the flocculation reactor, PASA is added. Agitation is milder in the flocculation
reactor than in the flash mixer.MEPC 57/2/2

ANNEX Page 6

I:\MEPC\57\2-2.doc In this way, flocs containi ng triiron tetraoxide and aggregated particles (SS, bacteria, plankton, etc.)
are formed in the untreated ballast water. Sin ce the floc contains trii ron tetraoxide, it is magnetically attractive at the next process, magnetic separator. Table 2-2 shows flocculation
time.

Table 2-2: Required time for fo rmation of flocs by coagulator

Item Required time Flash mixer 0.5 minutes (for micro floc formation) Flocculation reactor 2 minutes (for floc formation)

(The required time shown in Table 2-2 co rresponds to the amount of treatment at the rated operation of the ballast pump.)

2.2.4 Magnetic separator

The magnetic separator consists of a casing that receives the seawater containing flocs transferred from the coagulator and a magnetic disk array that remove s the flocs magnetically. The magnetic disk array consists of multiple magnetic disks in which permanent magnets are embedded (see Figure 2-5). While the ballast water is transferred from the coagulator, it flows through the magnetic disks, and the flocs are attract ed to the magnetic disks. The flocs attached to the disks are scraped off with scrapers in the open air and collected as sludge.

The coagulation magnetic separation method can remove flocs containing triiron tetraoxide within several seconds. Residual flocs are removed by filter separator described in the following
section.

Treated water Treated water Magnetic disk array

Sludge Rotating filter drum

Casing of magnetic separator Casing of filter separator Coagulator Magnetic separator Filter separator

Filter washing spray

Figure 2-5: Schematic di agram of magnetic separa tor and filter separator

2.2.5 Filter separator

The filter separator consists of a continuously ro tating filter drum, a casing, and filter washing sprays. The residue collected by filt er washing is returned to the ballast water feed pipe before the first chemical injection point s (see Figure 2-2) and is purified along with the unt reated ballast

water.MEPC 57/2/2

ANNEX

Page 7

I:\MEPC\57\2-2.doc 2.2.6 Sludge tank

The method being studied at present, after the temporary storage of flocs as sludge, is to handle the sludge on board and then unload it onto land. Since th e situation differs fr om ship to ship, it may be necessary to take individual measures.

The flocs collected in the magnetic separator are automatically tr ansferred to the sludge tank by conveyors without any manual handling. The stored sl udge is taken out of the ship for unloading after sufficient preparation such as transferring to individual contai ners or removing water, etc. In the unloading process, some steps such as tran sport of the indi vidual containers require manual handling. There is no human exposure in the re st of the steps sin ce they are automated.

2.3 Purification performance of the system

2.3.1 Quality of water treated by this system

The quality of the water treated (at a flow rate of 50 m 3 /h) by the pilot-scale set-up on reclaimed land in Tokyo Bay was measured by the amount of zoopla nkton, phytoplankton, and E. coli it
contained. The results meet the standards set in regulation D-2 for the discharge of ballast water (see Table 2-3).

Table 2-3: Results of organism removal performance

Item Unit Untreated

seawater * Treated

seawater Criteria

Plankton 50μm or larger Viable organisms / m 3 67,600 0 <10 10 - 50μm Viable organisms / ml 92.1 0 <10

E. coli MPN/100 mL 1,100 2 <250

Average data in the period from October 2006 to February 2007.

* Seawater taken from Tokyo Bay.

The quality of the water treated by this system was also measured by its SS concentration, using the same set-up as the organism removal perfor mance test mentioned above. The results show
that the SS concentration in the treated water of th e load test was the same as that of the control test (see Table 2-4).

Table 2-4: Results of SS removal performance

SS concentration (mg/L) Sample Untreated seawater Treated seawater
Control 1) 10 < 1
Load test 2) 50 < 1

Detection limit: 1mg/L 1) Actual seawater taken from Tokyo Bay on October 26, 2006. 2) Kaolin was added to the actual seawater before the treatment.MEPC 57/2/2

ANNEX Page 8

I:\MEPC\57\2-2.doc The following sections explain that the treated water by this system has no environmental and ecological risks.

2.3.2 pH of treated water

The treatment of seawater by the Hitachi Ballast Water Purification System slightly reduces the pH value of the treated water. This pH reduction is cau sed by reaction of PAC in water. PAC is a polybasic polyelectrolyte, and aluminium ions exist as an aqua-complex, [Al(OH 2 ) 6 ] 3+ , in which
six H 2 O molecules are co-ordinated around the alumin ium atom in octahedral configuration. The general formula of PAC is expressed by [Al 2 (OH)

n Cl 6-n ]
m (n: 1 to 5, m: 1 to 10). PAC reacts
with calcium carbonate in the untreated water to lo wer the alkalinity. Theref ore, the pH value of the water treated by the system will be reduced.

In this calculation, bicarboni c acid at 140 mg/L, determined from the standard seawater composition, is used as the alkalin ity of seawater. A pH value of 8.3, which is the intermediate pH value of the untreated seawater sampled fr om the purification expe riment carried out in Tokyo Bay, is used as the pH of th e untreated seawater. In theory, the pH is the lowest when m=1 and n=1, and it does not become much lower than 7.0. The pH value is 7.2 (for m = n = 1) under the condition of 5mg/L used for rated operation. The same results are obtained for m=2 to 10. Therefore, it is theoretically impossible for the pH value to become much lower than 7.0.

2.4 Application capacity

The volume of the major components of this system , particularly the volume of the coagulator, increases in proportion to the flow rate. This is because the retention time of the ballast water in the equipment, which is the treating time, is cons tant regardless of the flow rate. The treatment time of the coagulator and the ma gnetic separator can be kept c onstant regardle ss of the flow rate, and the tank volume inside these two devices is proportional to the flow rate of ballast water. On the other hand, the process scale of the filter separator is related to filter flux (filtration speed) and the fl ux can be kept constant. The area is proportional to the flow rate of the
ballast water.

The equipment can be scaled up or multiple sets of equipment can be installed in accordance with
the amount of ballast water to be treated. As a result, the commercial process scale would be designed at the ranges from 50 to 10,000 m 3 /h.

2.5 Specifications for chemicals

The following chemicals are used in the H itachi Ballast Water Purification System.

2.5.1 Triiron tetraoxide

.1 Identification of the chemical

Name of substance (IUPAC): triiron tetraoxide
Molecular formula or structural formula: Fe 3 O 4

.2 Quality standard for safety of human health

High purity grade is used.MEPC 57/2/2

ANNEX

Page 9

I:\MEPC\57\2-2.doc 2.5.2 PAC

.1 Identification of the chemical

Name of substance (IUPAC): Basic aluminium chloride Molecular formula or structural formula: [Al 2 (OH)

n Cl 6-n ]
m (n: 1 to 5, m: 1 to 10)

.2 Quality standard for safety of human health

The following requirements relating to impurities specified by ANSI/AWWA B408-03 Liquid Polyaluminium Chloride (AWWA, 2004) of the American Water Works Association (AWWA) Standard shal l be satisfied. The specifications of ìJapan Industrial Standard JIS K 1475 for poly aluminium ch lorideî (JIS, 1996) and ìEuropean Standard EN 883:2004 Chemicals used for treatment of water intended for human consumption-Poly aluminium chloride hydroxide and polyaluminium chloride hydroxide sulfateî (CEN, 2004) are stricter than that of ANSI/AWWA B408-03 Liquid Polyalumin ium Chloride. Poly aluminium chloride conforming to JIS or EN may be used.

2.5.3 PASA

.1 Identification of the chemical

Name of substance (IUPAC): Acryla mide sodium acrylate copolymer
Molecular formula or structural formula:

CH 2 CH CH 2 n CH

m

CONH 2 COONa

.2 Quality standard for safety of human health

The following requir ements relating to impurities sp ecified by ANSI/AWWA B453-06 Polyacrylamide (AWWA, 2006) of the (AWWA, American Water Works Association) Standard sh all be satisfied. ìJapan Water Works Association (JWWA, 1980) standard K 126-1980 for pol yacrylamide used for water worksî and ìThe European Standard EN 1407:1998 Chemicals used for treatment of water intended for human consumption- Anionic and non-ionic polyacrylamidesî (CEN, 1998) are similar quality standa rds. PASA conforming to JWWA or EN standard may be used.

3 HANDLING CHEMICALS ON BOARD SHIP

This section explains the procedure of loading chemicals onto ship, using chemicals for ballast water treatment and unloading sludge from ship to land.MEPC 57/2/2

ANNEX Page 10

I:\MEPC\57\2-2.doc 3.1 Carrying-in procedure and mechanism to pr event leakage of chemicals from piping

3.1.1 Triiron tetraoxide and PASA

Triiron tetraoxide and PASA powder are loaded onto the designated position on board packed in
a flexible container. The outlet of the container is connected to the inlet in the carry-in room and the triiron tetraoxide and PASA are poured to the onboard each dedicated tank respectively. To prevent scattering of the powder, the storage tank and piping equipped w ith safety valves are tightly sealed. An exhaust duct positioned close to the storage tank provides forced ventilation, preventing any spilled dust from scattering.

3.1.2 PAC

PAC liquid is loaded onto a designated position on board packed in an acid-resistant plastic
container. The container outlet is connected to the inlet in the carry-in room using an acid-resistant hose, and the safety valve is opened to pour the PAC to the on-board PAC storage tank. The storage tank is made of plastics or is lined with plastics on the inner surface to prevent
corrosion of the tank due to cont act with the acidic chemical. Th e feeding pipes connecting the PAC storage tank to the ballast wate r feed pipe are also made of aci d-resistant materials, such as plastic. If PAC leakage occurs, coamings with a height of about 10 cm around the PAC storage tank prevent the spread of the chemicals over th e floor, enabling the crew to safely and smoothly stop the leakage. In case the system is designe d to use PAC in powder form, the storage tank and hose connecting the PAC container to the inlet are made of plastics . To prevent the scattering of powder, the storage tank and pipi ng equipped with safety valves are tightly sealed. An exhaust duct providing forced ventilation is provided close to the storag e tank to prevent any dust from scattering if the powder spills.

3.2 Use of chemicals on ship and operation protocol

The chemicals used in the system are continuous ly injected from the piping of ballast water treatment equipment using three dedicated pumps. They are automatically controlled as part of
the automated operation of ballast water treatment. Si nce these chemicals are manually poured into the storage tanks by operators or crew, the operators wear goggles, masks, rubber gloves, and work clothes in anticipation of accidental chemical dispersion to prevent inhalation and adhesion of the dust to the skin. A notice regarding the use of appropriate protective gear is to be placed on the injector.

The flocs collected in the magnetic separator are automatically tr ansferred to the sludge tank by the conveyor without any manual hand lings. The part related to the sludge is basically covered so that the sludge does not scatter. The stored sludge is unloaded from the ship after sufficient preparations such as subdividing into individual containers or removing water with drum dryers, etc. In the unloading process, some steps partially require manual handling. Since the sludge contains chemicals, the operators should w ear goggles, rubber gloves, mask, and protective clothes. Warnings should be displayed on the devi ces to emphasize the need to use such safety

gear.MEPC 57/2/2

ANNEX Page 11

I:\MEPC\57\2-2.doc 4 ANALYSIS OF TREATED WATER

The treated water was tested to determine whether substances derived from the chemicals (triiron tetraoxide, PAC, and PASA ) used in the purification syst em were present and also to determine if harmful heavy metal were present (C ERI, 2007a). All tests we re carried out using a pilot-scale ballast water purification system (with a flow rate of 50 m 3 /h) on reclaimed land in Tokyo Bay. Actual seawater from Tokyo Bay was treated, and sa mples of untreated water and treated water were analysed.

4.1 Identification and determination of subs tances contained in raw and treated water

4.1.1 Test method

(1) Samples

The seawater was treated (marked ì(1)î in this s ection) at the pilot-scal e system mentioned above (flow rate of 50 m 3 /h) that is installed on reclaimed land in Tokyo Bay. The pilot-scale system simulates the ballast water purification system. Untr eated seawater (marked ì(2)î in this section) was pumped in at the location wher e the test equipment was installed.

(2) Amounts of additive chemicals

In this test, the chemicals were added at the rated concentrations (see Table 4-1).

Table 4-1: Amounts of additive chemicals (rated concentration)

Additive chemical Addition concentration (mg/L)
Triiron tetraoxide 30 PAC 5 (as Al)

PASA 1

(3) Water sampling

Samples of untreated water and treated water were taken from the respective sampling positions (see Figure 4-1).

Figure 4-1: Schematic diagram of water sampling positions Tokyo Bay Intake pump Treatment equipment Treated water tank Tokyo Bay

[Sampling the untreated water]

[Sampling treated water] Taken from the outlet of the rotary filter separator, which is the final stage of the system.MEPC 57/2/2

ANNEX Page 12

I:\MEPC\57\2-2.doc (4) Test item and method

Elemental analysis was done using inductively coupled plasma atomic emission spectrometry (ICP-AES) *

.

Volatile organic compounds: Purge and trap gas chromatograph-mass spectrometry

pH: JIS K 0102 12.1 Glass-electrode method
Arsenic: JIS K 0102 61.2 Atomic absorption spectrometry by hydride Aluminum: JIS K 0102 58.4 Inductively coupled plasma atomic emission spectrometry Manganese: JIS K 0102 56.4 Inductively coupled plasma atomic emission spectrometry Acrylamide: Gas chromatograph spectrometry Acrylic acid: Gas chromatograph mass spectrometry after solid-phase extraction and
derivatization Total organic carbon: JIS K 0102 22.2 Combusti on oxidation-infrared type TOC automatic analysis method

* The ICP methods used in JIS K 0102 correspond approximately to ISO 11885:2007; Water quality -- Determination of selected el ements by inductively coupled plasma optical emission spectrometry (ICP-OES).

Only the aluminium was measured for the samples taken both before and afte r the filtering with a glass and a membrane filter (see Table 4-2 and 4-3). All the othe r items were analysed for the samples taken before the filtering.

4.1.2 Test results

(1) Quantitative analysis of harmful heavy metals and water treatment agents (acrylamide, acrylic acid, aluminum)

Table 4-2: Results of quanti tative analysis of harmful me tals and water treatment agents Unit: mg/L

Sample
Test item (1)

Treated water (2)

Untreated water detection

limit PH 7.7(23.5oC) 7.9(23.5oC) - Arsenic (As) Not detected. 0.001 0.001 Aluminium (Al) 0.08 Not detected. 0.02
Manganese (Mn) 0.01 Not detected. 0.01 Acrylamide monomer Not detected. Not detected. 0.0001 Acrylic acid monomer Not detected. Not detected. 0.0001 Organic carbon (TOC) 1.3 1.3 0.5

* Cadmium(Cd), Lead(Pb), Mercury(Hg), Chromium(VI), and Selenium(Se) were not deteced
in both of treated water and untreated water.MEPC 57/2/2

ANNEX Page 13

I:\MEPC\57\2-2.doc Table 4-3: Comparison of aluminiu m content before and after filtration Unit: mg/L

Sample
Filter treatment (1)

Treated water (2)

Untreated water Detection

limit

Not filtered * 0.02 ND 0.02 Glass filter (1 μ m) ** ND ND 0.02 Membrane filter (0.45 μ m) ** ND ND 0.02

* In order to detect total aluminium in the sample (suspended aluminium in solid form and dissolved aluminium in ion form)

** In order to detect aluminium ions in the sample

(2) Qualitative and quantitative analyses of volatile organic compounds (VOCs)

Quantitative and qualitative analysis was conduc ted for the VOC compounds. Although scanning analysis was also conducted, no differences were detected between trea ted water and untreated

water.

(3) Qualitative analysis of semivolatile organic compounds

Each sample was extracted with dichloromethane and analysed by scanning measurement on a gas chromatograph-mass spectrometer. No subs tance was detected (detection limit: 0.002 mg/L as hexane equivalent).

(4) Elemental analysis by ICP-AES

A qualitative analysis was conducted on the treated water to find out whether the elements shown in Table 4-4. Since there was hardly any differe nce between the results of the treated water and the untreated water, the treated water does not seem to contain any new elements due to the processing of the Hitachi Ballast Water Purification System.

Table 4-4: Results of elem ental analysis by ICP-AES Unit: mg/L

No. Measured element (1)

Treated water (2)

Untreated water Detection

limit 1 Sodium (Na) 1,600 2,000 10 2 Magnesium (Mg) 760 750 0.01 3 Silicone (Si) 2 2 1 4 Sulphur (S) 1,300 1,300 10 5 Potassium (K) 330 330 5 6 Calcium (Ca) 78 79 0.1 7 Manganese (Mn) 0.1 Not detected. 0.1 8 Iron (Fe) Not detected. Not detected. 1 9 Strontium (Sr) 22 22 0.1

Remarks: Values are semiquantative (reference values).MEPC 57/2/2

ANNEX Page 14

I:\MEPC\57\2-2.doc 4.1.3 Amounts of substances derived from additive chemicals in treated water

Since the Hitachi Ballast Water Purification system uses triiron tetraoxide, PAC, and PASA as the chemicals, any iron, aluminium, or acrylamide detected in the treated water could possibly be
derived from the additive chemicals.

As shown in Tables 4-2 and 4-3, iron and acrylamid e were not detected in either the treated water
or the untreated water. Alumin ium was not detected in the unt reated water but 0.08 mg/L was detected in the treated water (see Table 4-2) . Since 5 mg/L (as Al) of PAC is added, the maximum ratio (%) of PAC contained in the treat ed water can be approximately to be 1.6% of
the PAC added.

4.2 Measurement of pH

4.2.1 Test method

(1) Samples

The samples for this test were prepared by purif ying seawater using the same equipment as used
for the identification and determinat ion tests (see Section 4.1.1 (1)).

(2) Amounts of additive chemicals

The amounts of chemicals used in this test were double those used under rated operating conditions (see Table 4-5).

Table 4-5: Amounts of additive chemicals

Additive chemical Additive concentration (mg/L)
Triiron tetraoxide 60 PAC 10 (as Al)

PASA 2

(3) Method

The pH measurement was started af ter the system was launched to ma ke sure all the devices were filled with water. Sampling of the treated water and untreated water was conducted 16 to 32 minutes after the start-up of treatment in the same way as described in Section 4.1.1 (3).

4.2.2 Results

The measurement was carried out within 10 minut es of sampling. As described in Section 2.3, the pH of the treated water was between 6.9 a nd 7.4 while the pH of the untreated water was between 8.0 and 8.6. Since the equilibrium is assume d to continue after trea tment, the pH of the
treated ballast water should not decrease until it is rel eased (in about two weeks).MEPC 57/2/2

ANNEX Page 15

I:\MEPC\57\2-2.doc 5 DATA SET

In this section, the iden tification of substances used in th e Hitachi Ballast Water Purification System and the data-set required for sect ion 4.2 of Procedure (G9) are reported.

As for the data of each substance, internationa l peer reviewed documents, databases, original study reports, etc. were searched comprehensively and broadly, a nd all the available data were
checked to evaluate their reliability. Only the data judged to be reliable have been adopted for this application.

5.1 Identification of substances or preparation (G9: 4.1)

5.1.1 Preparation (G9: 4.2.2)

No substance corresponding to the preparation de fined by paragraph 2.1.3 of Procedure (G9) is included in this system.

5.1.2 Active Substances

Triiron tetraoxide, PAC, and PA SA correspond to Active Substa nces (see Table 5-1). In this purification system, since almost all the additiv e agents collected in the flocs are removed (see 2.3.1), the amount of Active Substances releas ed into the environmen t together with the treated ballast water is negligible.

Table 5-1: Active Substances

Active
Substance 1 Active Substance 2 Active Substance 3

Name of
substance (IUPAC) Triiron
tetraoxide Basic aluminum chloride Acrylamide sodium acrylate coplymer

Synonym (used
in this document) Triiron
tetraoxide PAC PASA

CAS number 1317-61-9 1327-41-9 25085-02-3

UN number None None None Shipping name None None None Molar weight 231.53 Not applicable More than several million Empirical
formula or
structural
formula Fe 3 O 4 Al

n (OH)

m Cl (3n-m) 0<m<3n CH 2 CH CH 2 n CH

m

CONH 2 COONa

Purity 100% Percent of content: 10-11%
of water solution (aluminium oxide equivalent) 90% or more

Impurity None None Acrylamide monomer: 0.05% or less (CAS No. 79-06-1)

Stabilizers or
additives None None NoneMEPC 57/2/2

ANNEX Page 16

I:\MEPC\57\2-2.doc 5.1.3 Relevant Chemicals (G9: 2.1.4)

Since triiron tetraoxi de, PAC, and PASA do not have ac tive functional groups, no by-products are generated as a result of a reaction with seawat er. Consequently, no substance corresponding to a Relevant Chemical exists in this system.

5.1.4 Other substances

A substance that corresponds to ot her substances is acrylamide m onomers that remain in PASA as an impurity. Although its mass concentration is only 0.05% or less of PASA, a data survey was performed.

5.1.5 Configuration of PAC in water

Since PAC, which is the Active Substance in this system, can be transformed into water, its details are explained below.

PAC, which is used as an inorganic flocculating ag ent, is a polybasic polyelectrolyte. In water the aluminium ions take the form of the aqua-complex, [Al (H 2 O) 6 ] 3+ , in which six H 2 O molecules
are co-ordinated around the aluminium atom in octahedral formation. The general formula of PAC is expressed as [Al 2 (OH)

n Cl 6-n ]
m (n: 1 to 5, m: 1 to 10). The more detail is described in 2.3.2. The composition of this hydroxide is not well-defined, being a gel-like precipitate formed by the linkage of Al 3+ with OH - and being co-ordinated with many water molecules.

5.2 Data on effects on aquatic plants, invert ebrates and fish, and other biota, including sensitive representative organisms (G9: 4.2.1.1)

Since PAC is dissociated into ch loride ions and aluminium ions in an aqueous solution, and the aluminium ions exist as an aqua complex, as described before (5.1.5), its form in the water depends on pH values. Furthermore, since chloride ions exist in seawater in large amounts, the assessment of the ecotoxicity of PAC can be conducted based on the toxicity of aluminium.

In addition, collecting the data on the toxicity of aluminium ions is limited to the pH range of 6.5 to 7.5, which is actually applied in the co agulation sedimentation process of the Hitachi Ballast Water Purification System (see 2.3.2).

5.2.1 Acute aquatic toxicity

Triion tetraoxide

For triiron tetra oxide, there is a report on the use of fresh water fish, Japanese dace ( Leuciscus idus ), and the value of 48-h LC 0 is > 1,000 mg/L (EU, 2000a). There are no corresponding data available for algae and invert ebrates. Considering th at naturally-occurring
triiron tetraoxide is abundant in the environment and is not absorbed or accumulated in the body due to consisting of water insoluble particles, th e toxicity of triiron tetraoxide for algae and invertebrates is considered to be very low.MEPC 57/2/2

ANNEX Page 17

I:\MEPC\57\2-2.doc PAC

(1) Toxicity data on PAC is obtained from repor ts on algae, shellfish and fish. There is a report on the acute toxicity of PAC in algae using seaweed, and the 48-h LC 50 values are 1,500 mg/L and > 10,000 mg/L (growth inhib ition as the index), when the pH is not adjusted and adjusted to neutral, re spectively (Asada Ch emical Industry, 2003).

Regarding the acute toxicity of PAC in she llfish, there is a report on the study of Manila
clams in which the 48-h LC 50 values are 6,800 mg/L and > 10,000 mg/L, when the pH is not adjusted and adjusted to neutral, re spectively (Asada Chem ical Industry, 2003). As for the acute toxicity of PAC in fish, there is a report on the study of Oryzias latipes in
which the 48-h LC 50 values are 840 mg/L and > 10,000 mg/L, when the pH is not adjusted and adjusted to neutral, re spectively (Asada Ch emical Industry, 2003).

(2) Looking at the acute toxicity of PAC, data on water soluble aluminium salts such as
aluminium chloride can be examined to evalua te the toxicity of PAC in aquatic organisms
because the salts are dissociated in water an d form the same aqua complex as PAC. For aluminium ions, toxicity data ar e reported in invertebrates and fish.

For the acute toxicity of aluminium ions in invertebrates, the minimum 96-h LC 50 value is 0.097 mg Al/L for Ctenodrilus serratus , a sand worm marine species (IPCS, 1997; Petrich & Reish, 1979). Regarding th e acute toxicity of aluminium ions in fish, the minimum value of 96-h LC 50 in the pH range from 6.5 to 7.5, which is actually applied in the ballast water treatmen t, is 4.25 mg Al/L (pH: 7.4) for Pimephales promelas (IPCS, 1997).

PASA

Acute toxicity data on PASA are reported on inve rtebrates and fish. There is a report on the acute toxicity of PASA in invertebrates in which the fresh water species, Ceriodaphnia dubia is used,
and the 48-h LC 50 value is 218 mg/L (De Rosemond & Liber, 2004).

Looking at the acute toxi city of PASA, there is a report on the study of the marine species Girella punctata , and the 48-h LC 50 value is 840 mg/L (Tabata and Ishibashi, 1984). For fresh water species, there is a report on the study of Oryzias latipes

, Carassius auratus

, Cyprinus carpio , and Salvelinus namaycush , in which the LC 50 values are between 180 and >600 mg/L (Dia-Nitrix, 2004; Liver et al., 2005; Tabata and Ishibashi, 1984). Since the data provided by
Tabata and Ishibashi in 1984 are reliable be cause the testing methods and conditions are described in detail, the original report in Japanese has been translated into English and is listed in
the References.

No data on the toxicity in algae are reported. As PASA consists of pa rticles containing high molecular weight polymers (several millions or more), it is not absorbed and accumulated in the body. The toxicity of PASA in algae is considered to be low, not including any physical harmful
effect.MEPC 57/2/2

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I:\MEPC\57\2-2.doc Acrylamide monomers

Regarding the acute toxicity of acrylamide monomers in algae, there is a report on the fresh water green alga Pseudokirchneriella subcapitata , in which the 72-h EC 50 (growth inhibition as the index) is 33.8 mg/L (EU, 2002).

There is a report on the acute toxicity of acryl amide monomers in invertebrates in which the marine crustacean, Mysidopsis bahia , is used, and the 96-h LC 50 is 78 mg/L (EU, 2002). For fresh water fish, there is a report on Daphnia magna and chironomid species , and the 48-h EC 50 (swimming inhibition) is 98 mg /L for the former (EU, 2002).

As for the acute toxicity of acrylamide m onomers in fish, the minimum value of 96-LC 50 is 59 mg/L for Danio rerio (Kovriznych & Urbancikova, 2001).

5.2.2 Chronic aquatic toxicity

There are no chronic toxicity data available for triiron tetraoxide and PA C in aquatic organisms. Naturally occurring triiron tetraoxide is a bundant in the environment. Although it is highly possible that wild organisms are exposed to th is substance, no adverse effects have been identified. Therefore, it may be concluded that chronic toxicity of triiron tetr aoxide is not significant. For PAC, data on water soluble alum inium salts such as aluminium chloride are available for the evaluation of the toxicity of PAC in aquatic organisms because the salt
dissociate in water and form the same a qua- complexes as those formed by PAC.

PAC

To evaluate the toxicity of PAC in aquatic organi sms, data on water soluble aluminium salts such
as aluminium chloride can be examined because the salts are dissociated in water and form the same aqua complex as PAC. For aluminium i ons, chronic toxicity data are reported in
invertebrates and fish. As for the chronic toxicity of aluminium ions in invertebrates, there is a
report on Ctenodrilus serratus , a kind of sandworm, in whic h the 28-day NOEC for reproduction is 0.02 mg Al/L (pH: 7.6 - 8.0) (Petrich & Reish, 1979).

Looking at the chronic toxicity of aluminium ions in fish, ther e is a report on the fresh water species, Salvelinus fontinali s, in which the 60-day NOEC for growth is 0.088 mg Al/L (pH: 6.5 - 6.6) (IPCS, 1997).

PASA

Data on the chronic toxicity of PASA are reported on fish.

Regarding the chronic toxicity of PASA in fish, there is a report in which the fresh water species, Salvelinus namaycush is used, and the 30-day NOEC for activity is 75 mg/L and that for survival and growth is 300 mg/L (Liver et al., 2005).MEPC 57/2/2

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I:\MEPC\57\2-2.doc Acrylamide monomers

Data on the chronic toxicity of acrylamide monomers were gathered because traces of unpolymerized acrylamide monomers remain in PASA as an impurity. For acrylamide monomers, toxicity data are re ported in algae and invertebrate s. The chronic toxicity of acrylamide monomers in algae is 16 mg/L for a 72-hour NOEC in a growth inhibition test using the fresh water green alga, Pseudokirchneriella subcapitata (EU, 2002). There is a report on the chronic toxicity of acrylamide monomers in the invertebrate marine species, Mysidopsis bahia , in which the 28-day NOEC for death is 2.04 mg/L (Springborn Bionomics, 1985).

5.2.3 Endocrine disruption

There are no reports of triiron tetraoxide, PAC, PASA, and acrylamide monomers having an effect on endocrine disruption in aquatic organi sms. None of these substances are listed as suspected endocrine disruptors (MOE, 2005).

5.2.4 Sediment toxicity

There are no reports of triiron tetraoxide, PA C, or PASA having sedi ment toxicity. Triiron tetraoxide and PAC are inorga nic compounds. They are accumula ted and presented as triiron tetraoxide or aqua-complex ions of aluminium in the sediment. As all these substances are naturally occurring elements, the probability of their having an adverse effect on the sediment organisms is considered to be low.

Although PASA is accumulated in the sediment, it is not absorbed or accumulated in the sediment organisms because it consists of particles of high mol ecular weight polymers (several million or more). Therefore, the possi bility of PASA having an adverse effect on sediment organisms is considered to be low.

Data on the sediment toxicity of acrylamide monomers were gathered because traces of unpolymerized acrylamide monomers remain in PA SA as an impurity. Since acrylamide is biodegraded and mineralized easily, the possibility of acrylamide monomers being accumulated in the sediment is low. In addition, although acrylam ide monomers are water soluble (204 g/100 mL) (IPCS, 2000), both log K OW and soil adsorption coefficient, K OC, are low with values of -1.65 to -0.67 and 0.195 l/kg, respectively (EU, 2002). Theref ore, it is not absorbed or accumulated in the sediment and the possibility of adverse effects on sediment organisms is very low.

5.2.5 Bioconcentration

For PAC, data on water-soluble aluminium salts su ch as aluminium chloride may be examined to evaluate the bioconcentration of PAC in aquatic organisms because the salts dissociate in water and form the same aqua-complexes as those formed by PAC. In a test using Salvelinus fontinalis

, the value of BCF was 36 at pH 7.2 (Clevela nd et al., 1991). Although the concentration (0.2 mg/L) in this study was higher than the 60- day NOEC (0.088 mg Al/L) with growth as the index (pH 6.5 - 6.6) in the test in which Salvelinus fontinalis was used (see 5.2.2), it is reasonable to consider the result of that study, because it indi cated no effects at a pH of 7.2. In a test that used the marine species, Salmo salar , the BCF values at pH 5.5 were in the range of 76 to 190 (Buckler et al., 1995). Theref ore, the bioconcentration of aluminium ions was low.

As PASA consists of high molecular weight poly mers particles (several millions or more), it exhibits no biomembrane permeation and the possi bility of its accumulati on is low. The BCF values in a test using Cyprinus carpio are between 0.23 and 0.41, indicating that the
bioconcentration of PA SA is low (OEC, 2003).MEPC 57/2/2

ANNEX Page 20

I:\MEPC\57\2-2.doc For acrylamide monomers, when Cyprinus carpio and Oryzias latipes are exposed to water at concentrations of 1 mg/L and 10 mg/L for 20 days, the BCF values are 0.26 and 0.77 for Cyprinus carpio and 0.31 and 2.53 for Oryzias latipes (EU, 2002). In an exposure test of Oncorhynchus mykiss in water with a concentration of 0.710 mg/L, concentration and excretion reached a balance after 72 hours, and the BCF values are 1.44 and 1.65 for the whole body and internal organs, respectively (E U, 2002). These results indicate that the bioconcentration of acrylamide monomers is low.

No reports on the bioconcentration of triiron te traoxide were found. However, because it consists of water insoluble particles, trii ron tetraoxide is not absorbed or accumulated in living organisms
and has no bioaccumulation.

5.2.6 Food web/population effects

As the bioaccumulation of the chem icals used in this system is lo w, the possibility of secondary poisoning is low and no adverse e ffects on algae, invertebrates or fish are observed. Therefore, it
is assumed that none of these substa nces affect food webs or populations.

5.3 Data on mammalian toxicity (G9: 4.2.1.2)

5.3.1 Acute toxicity

Table 5-2: 50% lethal dose of triiron te traoxide, PAC, PASA, and acrylamide monomers

Exposure path Animal species End point Value Reference

Triiron tetraoxide
Oral
administration Rats LD 50 >10,000 mg/kg bodyweight EU, 2000a

PAC
Mice LD 50 Ca. 7,000 mg/kg EU, 2000b Oral
administration Rats LD 50 >2,000 mg/kg bodyweight EU, 2000b

PASA
Oral
administration Rats LD 50 >4,000 mg/kg bodyweight Cosmetic Ingredient Review, 2005 Acrylamide monomers Mice, rats, rabbits, and guinea pigs LD 50 150 - 180 mg/kg bodyweight ACGIH, 2001a Oral
administration

Mice and

rats LD 50 107 - 203 mg/kg bodyweight EU, 2002

Percutaneous
administration Rabbits LD 50 About 1,150 mg/kg bodyweight EU, 2002

* Although no data are available for the dermal route for triiron tetraoxide, PAC, or PASA, irritation is not caused by these substances or the extent of irritation is very low (see Section 5.3.2). Therefore, acut e dermal toxicity is consider ed to be weak, and only the
data on oral acute toxici ty are described below.MEPC 57/2/2

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I:\MEPC\57\2-2.doc 5.3.2 Effects on skin and eyes

Table 5-3: Skin irritation

Substance Species Method
Guidelines Result Reference/
Comments
Triiron
tetraoxide Rabbits OECDTG404 No EU, 2000a

Rabbits OECDTG404 No EU, 2000b Rabbits, mice, and pigs Not specified No EU, 2000b PAC

Humans Not specified Yes EU, 2000b PASA Rabbits Not specified No Cosmetic Ingredient Review, 2005 Rabbits Not specified No: for uninjured skin Very mild erythema and edema: for injured skin ACGIH, 2001a

Rabbits Not specified No or quite mild EU, 2002 Acrylamide

monomers

Humans Occupational

exposure Dermal irritation, skin separation EU, 2002

Table 5-4: Eye irritation

Substance Species Method
Guidelines Result Reference/
Comments
Triiron
tetraoxide No data No data No data It is expected that
triiron tetraoxide
causes no chemical
irritation because of its insolubility. Rabbits OECDTG404 Mild EU, 2000b PAC Humans Not specified Yes EU, 2000b PASA Rabbits Not specified Solid: Mild
5% water solution: No Cosmetic Ingredient Review, 2005 Rabbits Not specified 10% water solution: Mild
40% water solution: Yes ACGIH, 2001a Acrylamide

monomers Rabbits Not specified Yes EU, 2002MEPC 57/2/2

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I:\MEPC\57\2-2.doc 5.3.3 Sensitization

Table 5-5: Skin sensitization

Substance Species Method
Guidelines Sensitizer (yes/no) Reference/
Comments
Triiron
tetraoxide Guinea pigs Not specified No EU, 2000a

PAC Rabbits Not specified No EU, 2000b

PASA No data No data No It is not expected to exhibit any
sensitization because it is not absorbed in the body due to its high molecular weight. Acrylamide

monomers Guinea pigs Not specified Yes EU, 2002

Repeated dose toxicity (sub acute/subchronic toxicity).

5.3.4 Triiron tetraoxide

There is a report on intracavernous administration in rats over three weeks and intracavernous administration in dogs over three weeks which show s that pigment deposition increases in cells of the reticuloendothelial system but no injury in tissues occurs (EU, 2000a). Triiron tetraoxide is expected to have no adverse effects with repeat ed dose toxicity (subacu te/subchronic toxicity)
because it consists of insolubl e inorganic microparticles whic h are not absorbed in the body.

PAC

In an inhalation exposure test of 22 days in which PAC solutions of 0.34 μ g/L and 2.5 μ g/L were given to rats 4 hours a day at a frequency of 5 da ys a week, no toxicity or accumulation in tissues were observed (EU, 2000b).

PASA

No chronic toxicity was observe d in a test in which feedstu ffs containing 500 to 50,000 ppm of polyacrylamide were given to rats and dogs (Cosme tic Ingredient Review, 2005). PASA is expected to have no adverse effects with repeat ed dose toxicity (subacu te/subchronic toxicity) because it consists of high molecular weight pol ymer particles (several million or more) which are not absorbed in the body.

Acrylamide monomers

According to several tests by peroral administration to laboratory animals, the major toxic effects are on the nervous system and male generative organs. In a test in which feedstuffs containing 3 to 400 ppm of acrylamide monomers we re given to rats for 90 days, neurotoxicity appeared at 300 ppm or more, seminiferous epit helium degeneration app eared at 400 ppm, and the NOAEL was 110 ppm (corresponding to 5.5 mg/kg bodyweight/ day). In a test in which 0.05 to 20 mg/kg bodyweight/day of acrylam ide monomers contained in drinking water was given to rats for 90 days, neurotoxicity symptoms appeared at 1 mg/kg bodyweight/day or more, severe degeneration of peripheral nerv es appeared at 20 mg/ kg bodyweight/day, and theMEPC 57/2/2

ANNEX Page 23

I:\MEPC\57\2-2.doc NOAEL was 0.2 mg/kg bodyweight/day. The value in a peroral administration test for 90 days using rats with the minimal change of peri pheral nerves as the index was 0.2 mg/kg/day (ACGIH, 2001a).

There is a report of repeated exposure of acr ylamide monomers to humans causing adverse effects on the central nerve system, such as lo ss of muscle strength, disturbance of muscle co-ordination, gait abnorm ality, tremor, and hallucination (ACGIH, 2001a).

5.3.5 Chronic toxicity

Triiron tetraoxide

No data on chronic toxicity for la boratory animals are available. Chronic toxicity is not caused in humans because humans are only expos ed to triiron tetraoxide if an accident occurs when the chemical is being brought i n, and the duration of exposure is limited to a short period.

PAC

In several reports on inhalation exposure us ing laboratory animals, the accumulation of aluminium in the lungs, lymph nodes around the l ung alveoli, and adre nal glands, and lung disorders are reported. In tests in which rats and guinea pigs were exposed to three levels of PAC content, 0.25, 2.5, and 25 mg/m 3 for 6 hours a day at a frequenc y of five days a week for six months, the value of the NOAEL coul d not be obtained, the LOAEL was 0.25 mg/m 3 (EU, 2000b), lung injury occurred at a PAC concentration of 0.25 mg/m 3 or more, and an increase in weight was suppresse d at a concentration of 25 mg/m 3

.

PAC is widely used in the municipal purificat ion of water, and no adverse effects to human health have been identified. Therefore, the possibility of influence in humans is low.

PASA

Several tests have been conducted in whic h feedstuffs containing 500 to 100,000 ppm of polyacrylamide were given to rats for two years. No toxic effects or path ological changes related to the administration were observed in any of the tests (Cosmetic In gredient Review, 2005). Regarding chronic toxicity in humans, no a dverse effects have been observed on workers exposed to dust containing polyacrylamide (1 mg/m 3 ) over five years or more in polyacrylamide manufacturing plants (Cosme tic Ingredient Review, 2005).

Acrylamide monomers

There are several reports of tests on laboratory animals by pe roral administration, and the major
toxic effect is on the neural system. ACGIH has set the time-we ighted average threshold limit value (TLV - TWA) of acrylamide monomers to 0.03 mg/m 3 (ACGIH, 2001a).MEPC 57/2/2

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I:\MEPC\57\2-2.doc 5.3.6 Reproductive/developmental toxicity

Triiron tetraoxide

There are no data available on the reproductive and developmental toxicity of triiron tetraoxide. Triiron tetraoxide is not expected to have a ny adverse effects on reproduction and development
because it consists of insolubl e inorganic microparticles whic h are not absorbed in the body.

PAC

There is a report of a decrease in the number of implantations and fetal deaths observed in a test in which PAC was given by peroral admini stration to rats during day 7 to day 19 of pregnancy, in which the TDLo was 13,000 mg/ kg/day, but further details are unknown (EU, 2000b; U.S. NIOSH, 2007).

PASA

No effects on reproduction were observed in a three-generation test in which feedstuffs containing two levels of polyacrylamide, 500 and 2,000 ppm, were given to rats (Cosmetic Ingredient Review, 2005).

Acrylamide monomers

There are several reports of repr oductive toxicity in peroral admini stration to laboratory animals, and it has been shown that male genital toxicity and male sterility are caused. The value of the NOAEL with the effect on fertility potential was 5 mg/kg/day as for rats, and was 9 mg/kg/day as for mice (EU, 2002).

For developmental toxicity, there is a report of acrylamide monomers being given to pregnant female animals by peroral administration. Neither fetal toxicity nor tera togenicity is observed
with a dose that does not cause mo ther animal toxicity (EU, 2002).

5.3.7 Mutagenecity/genotoxicity

Triiron tetraoxide

In an in vitro reverse mutation test using Salmonella typhimurium (Ames test), the results were negative regardless of the existence of metabolic activation (EU, 2000a).

There are no in vivo reports available. Triiron tetraoxide is not expected to exhibit mutagenecity (genotoxicity) because it consists of insoluble in organic microparticles which are not absorbed in the body.

PAC

Although no reports on mutagenecity and genotoxicity are available, it can be assessed based on test data on aluminium chloride and so on, which exhibit behaviour identical to that of PAC in living organisms (formation of aqua-complexes). Negative results have been obtained in an

in vitro reverse mutation test (Ames test) using Salmonella typhimurium with aluminium sulfate as the test substance and a gene mutation test using L5178Y cells of the lymphoma of a mouse, but positive results have been obtained in a ch romosomal aberration test using human leukocytes
with aluminium sulfate as th e test substance (IPCS, 1997).MEPC 57/2/2

ANNEX Page 25

I:\MEPC\57\2-2.doc In two in vivo tests, one in which aluminium chlori de was given to mi ce by intraperitoneal administration and the other in which aluminium sulfate was given to rats, the induction of chromosomal aberrations in marrow cells was observed (IPCS, 1997).

PASA

Although no reports on the mutage nicity/genotoxicity of polyacryamide are available, since polyacrylamide is not absorbed by the body, it is not expected to exhibit mutagenicity/genotoxicity.

Acrylamide monomers

Among the in vitro tests, the results of mutation tests using bacteria were negative but the results of tests using animal cells were clearly positive in a micronucleus test, unscheduled DNA synthesis (UDS) test, and sister chromatid ex change (SCE) test. Acrylamide monomers are mutagenic substances that act directly on the ta rget, and there are many pieces of evidence of genotoxicity in body cells and generative cells in in vivo tests. In particul ar, it has been proved that transgenerational mutagenicity is indu ced in generative cells (ACGIH, 2001a; EU, 2002).

5.3.8 Carcinogenicity

Triiron tetraoxide

Several reports on the carcinogenici ty of triiron tetraoxide are available, all of which are insufficient to assess its carcinogenicity.

PAC

Although there are no reports ava ilable on the carcinogenicity of PAC, aluminium ions are an important factor as to the effects of PAC on liv ing organisms, and the assessment of PAC can be implemented on the basis of the carcinogenicity of aluminium com pounds that exhibit behaviour similar to that of PAC in living organisms. Among such aluminium compounds, several tests have been conducted relating to aluminium potassi um sulfate. For the two tests in which the increase in tumours was observed, since the te sts were conducted using a single dose, the dose dependency is not clear and nothing is described about the type of tumours or the organs with tumours. Therefore, the results of th ese tests do not suppor t the carcinogenicity.

PASA

Several tests have been conducted, in whic h feedstuffs containing 500 to 100,000 ppm of polyacrylamide were given to rats for two years, and feedstuffs containing 500 to 50,000 ppm of polyacrylamide were given to dogs also for two year s. In both of these tests, no lesions related to the administration were observed (C osmetic Ingredient Review, 2005).MEPC 57/2/2

ANNEX Page 26

I:\MEPC\57\2-2.doc Acrylamide monomers

There has been a test on the carcinogenicity of acrylamide, in which acrylamide monomers were given to F344 rats by drinking water administration for two year s, and an increase in the
incidence ratio of tumours in tissu es of various organs, such as thyroid gland, adrenal glands, and testis was observed. Judging from the types of tumours developed, a rela tionship with endocrine disruption is suggested. Furtherm ore, a relationship with the de velopment of brain tumours and spinal cord tumours is suggested although the ev idence is not sufficient. IARC has classified acrylamide monomers as Group 2A (probabl y carcinogenic to humans) (IARC, 1994).

5.3.9 Kinetics and metabolism

Triiron tetraoxide

There is a report that the clearanc e half-life period of a rat that ha s inhaled triiron tetraoxide for two hours is 47 days (EU, 2000a).

PAC

In an inhalation exposure test in which rats we re exposed to PAC for 24 months and guinea pigs for 21 months, aluminium was mainly accumulated in the lungs in both rats and guinea pigs, secondary to the adrenal glands in the rats and to the lymph nodes around the lung alveoli in the guinea pigs (EU, 2000b).

PASA

In a test in which polyacrylamide was given to rats by peroral administration, most of the acrylamide was recovered in feces and bowel conten ts and was not detected in the tissues, which shows that polyacrylamide is not absorbed in the body (Cosmetic Ingr edient Review, 2005).

Acrylamide monomers

Acrylamide monomers are rapidly absorbed oral ly and percutaneously by many animals so that unchanged substances and metabolites are widely distributed in liv ing organisms. In particular, they are distributed to the male reproductive organs and to unborn babies through the placenta. In rats and mice, acrylamide monomers are mainly excreted in urine after undertaking glutathione conjugation. Absorbed acrylamide monomers are also excreted in exhaled breath as carbon dioxide, while only small portion is excreted in feces (EU, 2002). In a test that used rats,
the selective accumulation in nerve cells was not observed (ACGIH, 2001a). There are only
limited data on the in vivo fate of acrylamide monomers in huma ns, and it has been indicated that acrylamide is absorbed orally or percutaneo usly because acrylamide monomer adducts are detected in hemoglobin (EU, 2002).MEPC 57/2/2

ANNEX Page 27

I:\MEPC\57\2-2.doc 5.4 Data on environmental fate and effe ct under aerobic and anaerobic conditions (G9: 4.2.1.3)

5.4.1 Degradation

5.4.1.1 Hydrolysis

Hydrolysis properties do not apply to triiron tetraoxide and PAC because they are inorganic compounds. Since the half-life period of acrylamid e monomers for hydrolysis is more than one year under the conditions of pH 5 to 9 and 55°C, acrylamide monomers are considered not to be easily hydrolyzed in environmental water (EU, 2002) . Therefore, it is assumed that PASA is resistant to hydrolysis, as in the case of acrylamide in environmental water.

5.4.1.2 Biodegradability

Biodegradability does not apply to triiron tetr aoxide or PAC because they are inorganic compounds. Regarding the biodegradability of PASA, th ere is a report on th e degradation rate of activated sludge taken from an urban sewage tr eatment plant using the coulometer method, in which PASA was assessed to be non-biodegra dable because it was hardly degraded after 300 hours (OEC, 2003).

The biodegradability of acrylam ide monomers has been tested based on OECD TG301D. Since the biochemical oxygen demand (BOD) values for 28 days under the two levels of the concentration of testing substa nce, 2 mg/L and 5 mg/L, were 100 and 53.3%, respectively, it has been determined that acrylamide monomers ar e easily degraded at lower concentrations (<2 mg/L) (EU, 2002).

5.4.2 Partition coefficient

A partition coefficient is not applied to triir on tetraoxide or PAC because they are inorganic compounds. Further, a partition coefficient is not a pplied to PASA because it is a high molecular weight polymer compound. The octanol/w ater partition coefficient (log P OW ) for acrylamide monomer is -0.67 to -1.65, and soil adsorption coefficient, K OC, is 0.195 l/Kg (EU, 2002).

5.4.3 Persistence and identification of main me tabolites in relevant media (ballast water, marine, and fresh water )

No generation occurs of degradation products fr om any of triiron tetr aoxide, PAC, and PASA. Since acrylamide monomers are resistant to hydr olysis and easily biodeg raded and mineralized under aerobic conditions, degrada tion products are not generated.

5.4.4 Reaction with organic matter

Triiron tetraoxide, PAC, PASA, and acrylamide m onomers all do not generate free radicals, and do not react with organic compounds.MEPC 57/2/2

ANNEX Page 28

I:\MEPC\57\2-2.doc 5.4.5 Potential physical effects on wildlife and benthic habitats

Triiron tetraoxice, PAC, PASA, acrylamide mono mers, and flocs would have no physical effect on the habitat of fish species, avian species , marine mammals or benthic organisms.

5.4.6 Potential residues in seafood

The substances used in this system do not e xhibit bioconcentration and so exhibit no potential persistence in seafood.

5.5 Physical and chemical properties for th e Active Substances and preparations and treated ballast water (G9: 4.2.1.4)

Table 5-6 shows the physicochemical properties of triiron tetraoxide, PAC, PASA, acrylamide monomers, and treated ballast water.

Table 5-6: Physicochemical properties

Triiron
tetraoxide PAC PASA Acrylamide

monomers Treated

ballast

water
CAS No. 1317-61-9 1327-41-9 25085-02-3 79-06-1 None Melting point (°C) 1,538 1) About -12 2) Not Applicable 84.5 1) NR 9)

Boiling point (°C) Not Applicable About 103 2) Not Applicable 125 at 3 kPa 1) NR

Flammability (Flash point for liquids ; °C) Not Applicable Noncombustible
5) None #1, 4) 138 (closed method) 3) NR

Density (20 °C; kg/m 3 ) 5,200 (5.2 g/cm 3 )
1) 1,340 (1.34 g/cm 3 ) 2) Bulk specific gravity; 0.55-0.65
4) 1,130(1.13 g/cm 3 )
3) NR

Vapour pressure (20 °C; Pa) Not Applicable Non-evaporable
5) Non-evaporable #2 1 3) NR

Vapour density (air = 1) Not Applicable Not Applicable Not Applicable 2.46 (calculated value) NR

Water solubility Insoluble 6) Soluble 1) Mixing with water forms highly viscous gel-like
material 4) 2,040,000 (25°C) (204 g/100 ml) 3) NR

pH in solution NR NR 4.3 (15%) 1) NR NR 7 - 7.3 (see 4.2)

Dissociation constant (pKa) Not Applicable No dissociable

group No dissociable

group No dissociable

group NR

Oxidationreduction potential Not Applicable None 5) None 4) None 7) None

Corrosivity to
material or equipment None Corrosive to
metals None None NoneMEPC 57/2/2

ANNEX Page 29

I:\MEPC\57\2-2.doc Triiron
tetraoxide PAC PASA Acrylamide

monomers Treated

ballast

water Reactivity to
container
material None None None None NR

Autoignition
temperature (°C) Not Applicable Noncombustible
5) None 4) 424 3) NR

Explosive properties Not Applicable None None None 7) NR

Oxidizing properties Not Applicable None 5) None 4) None 7) NR

Surface tension None Equal to water
because of

aqueous solution None None NR

Viscosity None 28 mPa.s (25°C)
2) Mixing with water forms highly viscous gel-like
material 4) 2.71 mPa.s (25°C) (50% aqueous solution) 8) 1.55cP (16°C)

Thermal stability Transformed
into iron
oxide (Fe 2 O 3 ) by heating in
air 1) Nonflammable Combustible by heating at high
temperature Violently polymerizes when
heated to over
85°C or when exposed to of light or oxidizing
agents. When heated to decomposition,
fumes and nitrogen oxide are generated. 3), 8) NR

Other physicochemical properties None None None Because acrylamide readily polymerizes, common products
contain polymerization
inhibitors 1) None

1) Merck, 2006, 2) EU, 2000b, 3) IPCS, 2000, 4) Dia-Nitrix, 2004, 5) Asada Chemical Industry, 2003, 6) Dean,1999, 7) EU, 2002, 8) HSDB, 2007, 9) NR: not required for G9
#1 Noncombustible under conditions of normal use (normal pressure, 0-50°C). #2 Non-evaporable under normal pressure and normal temperature because of high molecular weight polymers (several million or more).MEPC 57/2/2

ANNEX Page 30

I:\MEPC\57\2-2.doc 5.6 Analytical method at environmenta lly relevant concentration (G9: 4.2.1.5)

Triiron tetraoxide

The sample water is analysed by ICP emission spectroscopic analysis (ICP-AES) and detected as
iron ions.

PAC

The sample water is analysed by ICP emission spectroscopic analysis (ICP-AES) and detected as
aluminum ions.

PASA

The sample water is filtered with a membrane filter, and the infrared spectra of the substances on the filter paper is analysed by infrared spectromet ry (IR). Its spectra are compared with that of
the standard substance to know whether PASA is present or not. The substances gathered on the membrane filter are weighed on a scale to obtain the rough amount of PASA.

Acrylamide monomers

Acrylamide monomers in the sample water are brominated using potassium bromide solution and potassium bromate solution under acidic conditions to obtain dibromo-derivatives. Excess
bromine is reduced and eliminated with sodium th iosulfate, and the dibrom o-derivatives are then extracted with ethyl acetate. Trie thylamine is added to the solu tion to remove hydrogen bromide,
and the obtained monobromo-derivatives ar e analysed by gas chromatography (GC).

6 ECOTOXICITY STUDIES

In this section, the resu lts of ecotoxicity studies of saltwa ter representatives for three trophic levels (algae, invertebrates and fish) are presente d and the hazards of the ballast water treated by the Hitachi Ballast Water Purification System to the aquatic organisms are evaluated. (Refer to IDEA Consultants, Inc ., 2007a; 2007b; 2007c for more details.)

6.1 Methods of water treatment and water sampling

6.1.1 Set-up for Hitachi Ballast Water Purification System

The system used for the test was identical to the one used in section 4 Analysis of treated water (see 4.1.1 (1)).

6.1.2 Amounts of chemicals added to set-up

In order to evaluate the hazards of Active Substa nces to aquatic organisms, the substances were injected into the raw seawater to produce final concentrations two times higher than those of the standardized processing conditions for the Hitachi Ballast Water Purification System (Table 6-1).MEPC 57/2/2

ANNEX Page 31

I:\MEPC\57\2-2.doc Table 6-1: Final concentrations of chemicals after injection

Active Substance Concentration in untreated seawater (mg/L)
Triiron tetraoxide 60 PAC 10 (as Al)

PASA 2

6.1.3 Method of water sampling and water treatment procedure

Processing of seawater by the se t-up was carried out and supplied to the test facility daily from the day before the beginning of the toxicity tests to the last day of the tests. Approximately 20 L of the treated-seawater was sampled from the efflue nt in the outfall of the filter-separation unit when the processing had been carried out for 16 to 32 minutes (see 4.1.1 (3)).

6.2 Ecotoxicity testing

6.2.1 Testing on algae

(1) Test guidelines applied to the study

The toxicity study in algae wa s conducted according to the International standard ISO 10253 ìWater quality ñ Marine algae growth inhibition test with Skeletonema costatum and Phaeodactylum tricornutum , Second editionî (2006) and the US EPA guidelines ìShort-term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms, Third Editionî (2002). (Ref er to IDEA Consultants, Inc., 2007a for more details.)

(2) Test method and conditions

The marine diatom Skeletonema costatum was selected as the test sp ecies for this study, and the exposure experiment was conducted under the conditions shown below:

Type of exposure: Static, continuous shaking at 100 rpm Exposure duration: 72 hours Number of treatments: 5 treatment gr oups (1/1-, 1/2-, 1/4-, 1/8-, and 1/16- groups) and a control group Number of replicates: 3 replicates per treatment and 6 replicates for
control
Volume of test solu tion per vessel: 30 mL Initial cell density: 0.5 x 10 4 cells/mL Temperature: 20 ± 2 oC Illumination: Cool-white type fluorescent bulbs, continuous at 7,000 Lux ± 20%

(3) Results and conclusion

It is concluded that the ballast water treated by the Hitachi Ballast Water Purification System has no toxicity impact on the marine Diatom S. costatum without any dilutions.MEPC 57/2/2

ANNEX Page 32

I:\MEPC\57\2-2.doc 6.2.2 Testing on invertebrates

(1) Test guidelines applied to the study

The toxicity study on invertebrates was conducted according to the modified method reported by

Anasco et al

. 1) and the US-EPA guidelines ìShort-t erm Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms, Third Editionî (2002). (Refer to IDEA Consulta nts, Inc., 2007b for more details.)

(2) Test method and conditions

The marine gammarid Hyale barbicornis was used as the test spec ies in this study, and the exposure experiment was conducted under the conditions shown below.

Type of exposure: Semi-static , whole renewal every 24 hours Exposure duration: 21 days Number of treatments: 5 treatment groups (1/1-, 1/2-, 1/4-, 1/ 8- and 1/16-groups) and a control group Number of replicates: 20 replicates per group
Volume of test solu tion per vessel: 10 mL Test animal: Age; Neonates within 24 hours post-hatch Number exposed; 20 animals per group (one animal per vessel) Temperature: 24 ± 1oC Illumination: Cool-white type fluorescent bulbs, 14-hours light/10-hours dark Feeding: Artificial flake food Tetra MarineÆ (< 0.5 mm crushed pieces), once a day

(3) Results and conclusion

It is concluded that the ballast water treated by the Hitachi Ballast Water Purification System has no toxicity impact on the marine Gammarid H. barbicornis without any dilutions.

6.2.3 Testing on fish

(1) Test guidelines applied to the study

The toxicity study in fish was conducted in accordance with the OECD guidelines No.210 ìFish, Early-life Stage Toxicity Testî (1992) and th e US-EPA guidelines ìShortterm Methods for Estimating the Chronic Toxicity of Effluents a nd Receiving Waters to Marine and Estuarine Organisms, Third Editionî (2002). (Refer to IDEA Consultants, Inc., 2007c for more details)

1) Anasco N., Takenouchi A., Koyama J., Noro T., Imai S, Uno S. Toxicity of chemicals used to treat ballast waters (hydrogen peroxide and sodium hypochlorite) to four marine organisms., terminal report: Toxi city of Hydrogen peroxide and sodium hypochlorite to marine organisms, in preparation.MEPC 57/2/2

ANNEX Page 33

I:\MEPC\57\2-2.doc (2) Test method and conditions

The saltwater fish Java medaka, Oryzias javanicus , was selected as the test species for this study, and the exposure experiment was conduc ted under the conditions shown below

Type of exposure: Semi-static , whole renewal every 24 hours Exposure duration: From 1 day post- fertilization embryo to 28 days post-hatch
Number of treatments: 5 treatment groups (1/1-, 1/2-, 1/4-, 1/8-, and 1/16-group), and a control group Number of replicates: 3 replicates per group Volume of test solution per ve ssel: 100 mL (embryonic phase), 500 mL (post-hatch phase, until 14 days post-hatch), and 1,000 mL (post-hatch phase, after 14 days post-hatch) Test animal: Age; Fertilized eggs 1 day post-fertilization Number exposed: 60 eggs per group (20 eggs per vessel) Temperature: 26 ± 1 oC Illumination: Cool-white type fluorescent bulbs, 14-hours light/10-hours dark Feeding: Brine shrimp nauplii, once a day

(3) Results and conclusion

It is concluded that the ballast water treated by the Hitachi Ballast Water Purification System has no toxicity impact on the saltwater fish O. javanicus without any dilutions.

7 MATERIAL SAFETY DATA SH EET (MSDS) (G9: 4.2.7)

Samples of MSDS for triiron tetraoxide, PAC, a nd PASA are attached to the original assessment
report.MEPC 57/2/2

ANNEX Page 34

I:\MEPC\57\2-2.doc 8 RISK CHARACTERIZATION

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

Table 8-1 shows the results of an assessment of PBT. None of the triiron tetraoxide, PAC, PASA, and acryamide monomers are classified as PBT substances.

Table 8-1: Assessment of PBT

Low degradability (P) Bioaccumulation (B) Toxicity (T)
Half-life: >60 days in marine water, or >40 days in freshwater, or >180 days in marine sediment, or >120 days in freshwater sediment BCF > 2,000

or Log P OW ≥ 3 Chronic NOEC < 0.01 mg/L

Triiron
tetraoxide Not applicable * No No

PAC Not applicable * No No

PASA Yes No No Acrylamide

monomers No No No

* As described in 5.4.1, biodegradability and hydrol ysis do not apply to tr iiron tetraoxide and PAC because they are inorganic compounds.

8.2 Evaluation of treated ballast water (G9: 5.2)

To investigate the toxicity of the seawater treated by the H itachi Ballast Water Purification System, ecotoxicity tests were carried out on th ree types of marine. The seawater was treated (at a flow rate of 50 m 3 /h) by the land-based pilot set-up on reclaimed land in Tokyo Bay which
simulates the Hitachi Ballast Water Purification System, and was tested by adding twice as much of the three chemicals (triiron tetraoxide, PA C, and PASA) compared with rated operation. All the ecotoxicity studies with the treated ballast water as a test substance were conducted under the conditions specified by the OECD princi ples of Good Laboratory Practice and were performed according to interna tional standards such as OECD test guidelines or US EPA guidelines. (For details, see section 6.)

The above test results show that seawater treated with the addition of chemicals in rated operation does not have any adverse effect on ma rine organisms even if released without dilution, because seawater treated with twice as much chemical as in the rated operation does not influence marine organisms at all even if released without dilution (100%).MEPC 57/2/2

ANNEX Page 35

I:\MEPC\57\2-2.doc 8.3 Risk characterization and analysis

8.3.1 Reaction with organic matte r (G9: 4.2.1.3; this report 5.4.4)

Since triiron tetraoxide, PAC, a nd PASA all do not generate free ra dicals, they are not reactive with organic matter.

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

Since triiron tetraoxide and PA C are inorganic substa nces, hydrolysis and biodegradability are not applicable. Acrylamide monome rs are resistant to hydrolysis but biodegraded in a relatively short period. PASA is considered to be resistan t to hydrolysis. In addition, PASA is scarcely biodegraded in activ ated sludge after 300 hours and is therefore not biodegradable.

In the Hitachi Ballast Water Purification System, since almost the entire additive chemicals are collected in the flocs, the amount of Active Substances released into the environment together with the treated ballast water is negligible. Ther efore, the characteristic s described here do not
have a serious environmental effect.

8.3.3 Prediction of discharge and environmental concentrations

Table 8-2: Summary of predicte d discharged concentration PEC

Predicted concentration at discharge (mg/L) PEC (mg/L)
Triiron tetraoxide 0.69 <0.69

PAC 0.15 <0.15 PAC (aluminium ions) 0.01 <0.00358 *

PASA 0.016 <0.016 Acrylamide monomers 0.00005 <0.00005

* Estimation of environmental concen tration based on the MAM-PEC Model.

The environmental concentration when the treated ballast water is discharged in Rotterdam Port was estimated using the MAM-PEC Model (version 1.6). It is assumed that all ships entering Rotterdam Port are provided with the Hitachi Ballast Water Purification System.

The concentration of original aluminium ions in the seawater of Rotterdam Port, which is the background concentration, is a ssumed to be 0.035 mg/L based on the value shown in the reference (Kobayashi et al., 2006) . Table 8-3 shows the results of the estimation. The average
concentration in the water is calculated to be 0.00350 mg/L, which is the same as the background concentration. Therefore, it is concluded that alum inium ions in the ballast water discharged from the Hitachi Ballast Water Purification System do not have an influence on the environmental concentration. (CERI, 2007b).MEPC 57/2/2

ANNEX Page 36

I:\MEPC\57\2-2.doc Table 8-3: Estimated concentratio ns in water using MAM-PEC Model

Item Concentration of Aluminium ions (μg/L) Maximum concentration 3.58 (0.00358 mg/L) Average concentration 3.50 (0.00350 mg/L)

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

As described in section 5.2.5, the subs tances are not bioaccumulative.

8.3.5 Effects assessment (G9: 5.3.9)

Triiron tetraoxide

The data on ecotoxicity of triir on tetraoxide do not correspond to the GHS acute toxicity hazard
category.

PAC

The data on ecotoxicity of PAC do not correspon d to the GHS acute toxicity hazard category.

PASA

The data on ecotoxicity of PASA do not correspond to the GHS ac ute toxicity hazard category.

Acrylamide monomers

The data on ecotoxicity of acrylamide monomers correspond to the GHS acute toxicity hazard category III (harmful). But, ac rylamide monomers contained as an impurity in PASA account for 0.05% or less of PASA by weight as give n in 2.5. As a result, the acrylamide monomer
concentration in ballast water is 0.0005 or less mg/L (before magnetic separation). Because the acrylamide monomer concentration in the treated water is 0.0001 or less mg/L as given in 4.1.2, the risk to aquatic organisms is negligible (see 9.3 for details).MEPC 57/2/2

ANNEX Page 37

I:\MEPC\57\2-2.doc 8.3.6 Derivation of Predicted No -Effect Concentration (PNEC)

Table 8-4: PNECs

Toxicity (mg/L) Assessment
factor PNEC (mg/L)
Triiron
tetraoxide 48-h LC 0 (acute) > 1,000 1000 > 1 PNECshort

PAC 48-h LC 50 (acute) 840 1000 0.84 PNECshort

96-h LC 50 (acute) 0.097 1000 0.003597 a) PNECshort PAC (aluminium ions) 28-day NOEC (chronic) 0.02 1000 0.00352 a) PNEClong

48-h LC 50 (acute) 180 1000 0.18 PNECshort PASA 30-day NOEC (chronic) 75 100 0.75 PNEClong

96-h LC 50 (acute) 59 1000 0.059 PNECshort Acrylamide

monomers 28-day NOEC (chronic) 2.04 100 0.02 PNEClong

a) The natural background concentration is added.

Since the PNEClong is smaller than the PNEC short for PAC (aluminium ions), PASA, and acrylamide monomers, PNEClong is applied in the PEC/PNEC ratio described in section 9.3.1.

9 RISK ASSESSMENT

9.1 Risk to ship safety

9.1.1 Risk during the storage of chem icals and operation of equipment

The IBC code is not applied to tr iiron tetraoxide, PAC, or PASA.

As seen from the physical properties descri bed in 5.5, triiron tetrao xide, PAC, PASA, and acrylamide monomers are not corrosive, do not react with the storag e tank, do not ignite spontaneously, do not vaporize, and do not have oxidizing properties under the assumed on-board circumstances. Therefore, there is no con cern that this substance may cause an accident such as corrosion, spontaneous ignition, or explosion of the vesselís body and on-board structures during the storage or operation of the equipment.

9.1.2 Risk from the treated ballast water

The treated ballast water is not corrosive, and the concentrations of volatile and semivolatile substances are comparable to those in the seawater of the reference site as described in 4.1.2 (2) and 4.1.2 (3). Therefore, there is no concern about accidents occurri ng in the ballast tank.MEPC 57/2/2

ANNEX Page 38

I:\MEPC\57\2-2.doc 9.2 Risk to human health (sailors)

9.2.1 Exposure to humans

Since the operation of the Hit achi Ballast Water Purification System is automated from the chemical injection into the ballast water through to the sludge tr ansfer into the sludge tank, no manual operation by the crew is required and no dedicated oper ators are necessary.

External to the purifying operation, there are small potential risks of short-time exposure to humans because some manual operation is required for pouring the chemicals into the storage tank, preparing for unloading the sludge, and actually unloading th e sludge onto land.

When the chemicals are poured into the storage tanks , the transfer is from one closed container to another closed container, so the risk of exposure is minimal. The operator must wear safety gear such as goggles, rubber gloves, and a mask in anticipation of accidents such as powder being scattered. Warnings should be displayed on the equipment of this system to emphasize the need to use such safety gear.

9.2.2 Risk to human health

As described in 5.3, triiron tetraoxi de is not a toxic substance. Fu rthermore, the only operations that may cause exposure to humans are the pouring of chemicals into the storage tank, preparing for unloading the sludge, and unloading the sludge onto land. In these operations, the potential exposure periods are limited and the workers wear pr otective gear, so there is virtually no risk to
human health.

PAC is not toxic, as described in 5.3, but it is an irritant and has been shown to have adverse effects in reproductive/developmen tal toxicity tests on animals. Therefore, the Hitachi Ballast Water Purification System minimizes the risk to human health by using PAC conforming to the standards for water purification chemicals estab lished by the American Water Works Association (AWWA) and by automating the pur ification operation. The only operations that may cause exposure to humans are the pouring of chemicals into the storage tank, pr eparing for unloading the sludge, and unloading the sludge onto lan d. In these operations, the potential exposure periods are limited and exposure is prevented by protective gear. Furthermore, the frequency of these operations is limited so there is virtually no risk to human health.

As described in Section 5.3, PASA is not a toxic substance. The Hitachi Ballast Water Purification System minimizes the risk to human health by using PAC conforming to the standard for water purification chemicals establ ished by the American Water Works Association and by automating the purification operation. The only operations that may cause exposure to humans are the pouring of the ch emicals into the storage tank, preparing for unloading the sludge, and unloading the sludge ont o land. In these operations, the exposure periods are limited and exposure is prevented by protective gear. Furt hermore, the frequency of these operations is
limited so there is virtuall y no risk to human health.

The risk of acrylamide monomers to human h ealth was investigated because traces of unpolymerized acrylamide monomers remain in PA SA as an impurity. However, the PASA used in the system conforms to the standard for water purification chemicals established by the
American Water Works Associatio n. The level of contamination is 0.05% or less, which has been proven safe. It poses virtually no risk to human health.MEPC 57/2/2

ANNEX Page 39

I:\MEPC\57\2-2.doc 9.3 Risk to aquatic environment

9.3.1 Assessment by PEC/PNEC ratio

An assessment by PEC/PNEC ratio was carried out on triiron tetraoxide, PAC, PASA, and acrylamide monomers. The assessment for PAC wa s conducted by using the acute toxicity data
for PAC and aluminium ions and the chr onic toxicity data for aluminium ions.

As derived in 8.3.6, the PNEC values are > 1 mg/L for triiron tetr aoxide, 0.84 mg/L for PAC, 0.003597 mg /L for PAC (a luminium ions), 0.18 mg/L fo r PASA, and 0.02 mg/L for acrylamide monomers (see Table 8-4).

As derived in 8.3.3, the PEC values are 0.69 mg/L for triiron tetraoxide, 0.3 mg/L for PAC, 0.00358 mg /L for PAC (aluminium io ns), 0.016 mg/L for PASA, and 0.00005 mg/L for acrylamide monomers (see Table 8-2).

From the above data, the PEC/PN EC ratio values are derived. The PEC/PNEC ratios are <1 for triiron tetraoxide, PAC, PASA and acrylamide monomers, which s hows that there is virtually no risk to aquatic organisms.

At this moment, the PEC/PNEC ratio for PAC (alu minium ions) is not lo w enough to be assessed as having no effect on the aquatic environment. Ho wever, the analysis of treated water described
in section 4.1 was carried out before the floccu lation technique was fully developed. It has been confirmed that the amount of flocs remaining in the water treated by the current improved structure is drastically less than the amount remaining in the water treated by the previous structures. Since detailed improvements on the eq uipment are ongoing, new da ta on water quality will be collected and shown in the application for final approval.

Table 9-1: PEC/PNEC ratio

PEC (mg/L) PNEC (mg/L) PEC/PNEC
ratio
Triiron tetraoxide 0.69 > 1 < 0.69

PAC 0.15 0.84 0.18 PAC (aluminium ions) 0.00358 0.00352 1.02

PASA 0.016 0.18 0.09 Acrylamide monomer 0.00005 0.02 0.0025

9.3.2 Assessment of treated ballast wat er by ecotoxicity test (G9: 5.3.14)

A chronic ecotoxicity test was conducted based on GLP principles and in accordance with test guidelines established by OECD, ISO, and USEPA to assess the effects of ballast water treated by the Hitachi Ballast Purificati on System on aquatic organisms (for details, see section 6).MEPC 57/2/2

ANNEX Page 40

I:\MEPC\57\2-2.doc As described in 6.1.2, since the concentration of chemicals added was twice that of rated concentration, the volume of substances containe d in the treated water supplied for the testing was twice of the predicted concentration descri bed in 8.3.3. Consequently, the concentrations of each substances are expected 1.38 mg/L for triiron tetraoxide, 0.3 mg/L for PAC, 0.02 mg /L for aluminium ions, 0.032 mg/L for PASA, a nd 0.001 mg/L for acrylamide monomers.

Table 9-2 shows the NOEC values derived from the results of the chronic ecotxicity test.
The 100% concentration treated ballast water a ffected none of the organisms examined. Given that the quantities of chemicals added in the rated operation of the Hitachi Ballast Purification System are half of those added in the test, it is concluded that the trea ted water under the rated conditions has virtually no e ffect on aquatic organisms.

Table 9-2: NOEC of treated ballast water

Test substance Classific
ation of organism Organism species End point Toxicity (Maximum no
observed effect concentration) Algae Skeletonema

costatum NOEC for
72 hrs 100% treated
ballast water *

Invertebr

ates Hyale
barbicornis NOEC for 21 days 100% treated
ballast water * Treated ballast water (containing triiron tetraoxide; 1.38 mg/L, PAC; 0.3 mg/L, aluminium ions; 0.02 mg/L, PASA; 0.032 mg/L, acrylamide monomers; 0.0001 mg/L) Fish Oryzias javanicus NOEC for 40 days 100% treated
ballast water *

* These findings conclusively demonstrated that ballast water treated by the Hitachi Ballast Water Purification System has virtua lly no impact on aquatic organisms.MEPC 57/2/2

ANNEX Page 41

I:\MEPC\57\2-2.doc REFERENCES

ABC Labs (Analytical Bio-Chemistry Laboratorie s) (1983a) Dynamic 96-hour acute toxicity of acrylamide monomer to fathead minnow ( Pimephales promelas ). EPA Doc. I.D.40-8331545,

OTS0507315.

ABC Labs (Analytical Bio-Chemistry La boratories) (1983b) Dynamic 96-hour acute toxicity of acrylamide monomer to midge larvae ( Paratanytarsus parthenogenetica ). EPA Doc. I.D.40-8331546, OTS0507316.

ABC Labs (Analytical Bio-Chemistry Laboratorie s) (1983c) Dynamic 96-hour acute toxicity of acrylamide monomer to bluegill sunfish ( Lepomis macrochirus ). EPA Doc. I.D.40-8331544,

OTS0507314.

ABC Labs (Analytical Bio-Chemistry Laboratorie s) (1983d) Dynamic 96-hour acute toxicity of acrylamide monomer to rainbow trout ( Salmo gairdneri ). EPA Doc. I.D.40-8331547,

OTS0507317.

ACGIH (2001a) American Conference of Govern mental Industrial Hygienists, Acrylamide.
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OH.

ACGIH (2001b) American Conference of Govern mental Industrial Hygienists, Iron oxide.
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Anasco N., Takenouchi A., Koyama J., Noro T., Im ai S, Uno S. Toxicity of chemicals used to treat ballast waters (hydrogen peroxide and so dium hypochlorite) to f our marine organisms, terminal report: Toxicity of Hydrogen peroxide and sodium hypochlorite to marine organisms, in preparation.

Asada Chemical Industry. (2003) Material Safety Data Sheet for Poly Aluminium Chloride.

ATSDR (2006) Agency for Toxic Substances and Disease Registry, Draft Toxicological profile for aluminium, Atlanta, GA. 91-92.

AWWA (2004) American Water Works A ssociation, ANSI/AWWA B408-03 Liquid Polyaluminium Chloride.

AWWA (2006) American Water Works Associ ation, ANSI/AWWA B453-06 Polyacrylamide.

Baart, A., Boon, J.and Hattum, B. (2002) Us er-manual-quick guide MAM-PEC Version 1.4.

Bengtsson, B.-E. (1978) Use of a harpacticoid c opepod in toxicity tests. Mar. Pollut. Bull., 9, 238-241.

Biesinger, K.E. and Christensen, G.M. (1972) E ffects of various metals on survival, growth, reproduction, and metabolism of Daphnia magna. J. Fish. Res. Board Can., 29, 1691-1700. Buckler, D.R., Mehrle, P.M., Cleveland, L. and Dwyer, F.J. (1987) Influence of pH on the toxicity of aluminium and other in organic contaminants to east co ast striped bass. Water Air Soil Pollut., 35, 97-106.MEPC 57/2/2

ANNEX Page 42

I:\MEPC\57\2-2.doc Buckler, D.R., Cleveland, L., Little, E.E. a nd Brumbaugh, W.G. (1995) Survival, sublethal responses, and tissue resi dues of Atlantic salmon exposed to acidic pH and aluminum. Aquat. Toxicol., 31, 203-216.

CEN (1998) European Committee for Standardi zation, European Standard EN 1407, Chemicals
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