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

I:\MEPC\58\2-2.doc

INTERNATIONAL MARITIME ORGANIZATION

IMO 

# E

MARINE ENVIRONMENT PROTECTION COMMITTEE 58th session Agenda item 2 MEPC 58/2/2 20 March 2008 Original: ENGLISH

HARMFUL AQUATIC ORGANI SMS IN BALLAST WATER

Application for Basic Approval of the Ecochlor Æ Ballast Water Treatment System

Submitted by Germany

SUMMARY

Executive summary: This document contains the non-conf idential information related to the application for Basic Approval of the Ecochlor Æ Ballast Water Treatment System in accordance with the Procedure for approval of ballast water management systems that make use of Active Substances (G9) adopt ed by resolution MEPC.126(53)

Strategic direction: 7.1

High-level action: 7.1.2

Planned output: 7.1.2.4

Action to be taken: Paragraph 5

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

Introduction

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

2 The Procedure for approval of ballast water management systems that make use of Active Substances (G9) stipulates the requ ired information (MEPC 53/24/Add.1, annex 4, paragraph 4.2.1) and provis ions for risk characteri zation and analysis (M EPC 53/24/Add.1, annex 4, paragraph 5.3), which, according to section 6 of Procedure (G9), should be evaluated by the Organization.

3 The receiving competent authority in Germany has verified the application dossier and believes it to satisfy the data requirements of Procedure (G9) adopted by resolution MEPC.126(53).MEPC 58/2/2 - 2 -

I:\MEPC\58\2-2.doc 4 In accordance with BWM.2/Circ.12, Germany th erefore submits the non-confidential part of the manufacturerís application dossier in the annex to this document. The complete dossier will be made available to the experts of the GESAMP-BWWG with the understanding of confidential treatment.

Action requested of the Committee

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

***1

1.0 INTRODUCTION

The Ecochlor ® Ballast Water Treatment System (BWTS) applies esta blished chlorine dioxide technology to oxidize and disinfect aquatic invasiv e species (AIS). Chlorine dioxide has a long history (50+ years) of being applied safely and eco nomically for the control of microorganisms in industrial and municipal waters. What is unique about chlorine dioxide is its ability to be effective against a wide range of troublesome organ isms and in a broad range of water quality conditions. A second unique feature of the chlorin e dioxide generated with the Ecochlor ®

BW T S compared to other oxidants (such as chlorine) is the minimization of unwanted by- p r od u c t s

.
Chlorine dioxide is believed to be a superior candi date for ballast water treatment for the following reasons:

• Chlorine dioxide oxidation is well documented in drinking water applications; • Chlorine dioxide kinetics of bacterial disinfecti on are fast; • Chlorine dioxide inactivates organisms at low dos ages (a favorable C x t); • Chlorine dioxide generated with the E cochlor ® BW T S does not produce chlorinated by- p r odu c t s ; • Chlorine dioxide does not significantly increase corrosion rates at the concentration used with the Ecochlor ® BWTS; • Chorine dioxide is documented as an effective bio cide against known pathogens that demonstrate resistance (i.e. Cryptosporidium , anthrax, etc.); • Chlorine dioxide can be safely and economically p roduced onboard ship; • Chlorine dioxide is uniquely effective in prevent ing and neutralizing biofilm; and • Chlorine dioxide typically decays to below detect ion levels in a relatively short time period.

Ecochlor is applying for Basic Approval of the Pura te ® chlorine dioxide generation method utilized with the Ecochlor ® BWTS in accordance with the International Maritime Organization ( I M O ) G u i d e li n e 9 ( r e s o l u ti on M E P C

. 126 ( 53 ))

. T h i s a pp li ca ti on w a s c o m p il e d u s i n g t h e g u i d a n ce a nd f

o r m a t p r o v i d e d i n t h e D r a f t M e t h o d o l o g y ( M E P C 55 / 2 / 16

, a nn e x 4 )

. 1.0.1 Technology Overview
The Ecochlor ® BWTS generates chlorine-free chlorine dioxide usin g the Eka Chemicals Purate ® technology, a patent-protected chlorine dioxide gen eration method. Eka’s Purate ® technology is a chlorate-based chlorine dioxide generation proces s. This method differs from other conventional chlorine dioxide generation methods th at involve use of aqueous or gaseous chlorine, making the chlorine-free Purate ® method environmentally superior. Additionally, Eka’s Purate ® technology produces chlorine dioxide efficiently, thereby controlling the required input of precursor chemicals and eliminating produc tion of unwanted by-products.

To further explain the chemistry, chlorine dioxide can be generated using differing methods, and a number of chlorate ion reduction processes exist to produce chlorine dioxide. Some of these methods can also produce chlorine as a generation i ntermediate or by-product (e.g., Mathieson, Solvay, R2 and R3/SVP processes). To avooid the ch lorine by-product in these traditional methods, a new process was developed where hydrogen peroxide is the reducing agent and2

hydrochloric acid is replaced by sulfuric acid. Th is newer process, utilized in the patentprotected Eka Chemicals Purate ® technology employed with the Ecochlor ® Ballast Water Treatment System (BWTS), does not involve or create free available chlorine (FAC).

Additionally, it is important to note that chlorine dioxide and chlorine act very different chemically. For instance, chlorine dioxide is an o xidant, yet it does not chlorinate. In contrast, FAC is both an oxidant and a chlorinating agent. B ecause FAC is not present in any detectable concentration, the application of chlorine-free chl orine dioxide results in oxidation without the direct formation of organic by-products such as tri halomethanes (THM’s), and other unwanted by-products such as haloacetic acids (HAA’s) are mi nimized.

To support the above statement regarding halogenate d by-products, Ecochlor presents theoretical discussion of the chlorine-free Purate ® chlorine dioxide methodology as well as chemical analysis of treated ballast water from San Francisc o Bay that demonstrates that chlorine dioxide does not directly form THM’s.

Using the preparation chemicals, the Ecochlor ® BWTS generates and injects a dilute solution of chlorine-free chlorine dioxide directly into ballas t water as it is loaded onboard. Treatment of ballast water occurs during uptake only. The chlor ine dioxide solution is not stored onboard as a concentrated chemical at any time. It is generated on demand based on the amount of ballast water being pumped onboard. After injection into t he incoming ballast water, chlorine dioxide remains effective in the ballast water tanks for a short period (2 – 20 hours) in order to neutralize ballast tank biofilm that can cause bacterial re-gr owth. Over time, the chlorine dioxide continues to react and/or decay in the ballast tanks so that at the time of discharge the ballast water contains an undetectable concentration of chlorine dioxide. Operational specifics of the Ecochlor ® BWTS are discussed in detail in Section 3.0.1, Manner of Application.

Since 2001, several bench scale experiments have be en conducted on the use of chlorine-free chlorine dioxide to control aquatic invasive specie s. The success of the bench scale studies and the proven effectiveness of chlorine dioxide in num erous land-based water disinfection applications indicated that the technology was read y for land-based efficacy testing. However, because there were no land-based testing facilities available in the world, Ecochlor proceeded directly to installing a full-scale system on the Atlantic Compass in 2004 for efficacy testing. A second prototype system was installed on the M/V Moku Pahu in 2005. Testing of these systems is ongoing to demonstrate and verify the efficacy o f the Ecochlor ® BWTS. Shipboard testing is being conducted by scientists at the University Of Rhode Island, Graduate School of Oceanography (URI) who are using a testing protocol approved by the United States Coast Guard (USCG). Ballast water treated with the Ecoch lor ® BWTS will comply with the performance standards in Regulation D-2 of the Inte rnational Convention for the Control and Management of Ship’s Ballast Water and Sediments, a s well as standards proposed in the United States Ballast Water Management Act of 2005 (Senate Bill S.363).

The Ecochlor ® BWTS is viable for all ballast water capacity rang es, and is distinguished by the system’s capability to treat at high ballast water flow rates. The Ecochlor ® BWTS can be installed as a retrofit on existing vessels or duri ng a new construction, with the latter being the3

most straightforward and cost effective. Additiona lly, Ecochlor’s treatment system can be easily incorporated into a land-based system to treat ball ast water land-side.

2.0 IDENTIFICATION OF PREPARATIONS, ACTIVE SUBSTANC ES AND RELEVANT CHEMICALS (G9: 4.1)

Based on the definitions of Preparations, Active Su bstances and Relevant Chemicals in the G9 procedure (Resolution MEPC.126(53)), Ecochlor class ifies the substances involved in the Ecochlor ® BWTS process as follows:

Preparations: There are two preparation substances used with th e Ecochlor ® BWTS:

1) Purate ® (a proprietary formulation from Eka Chemicals cont aining 40% by weight sodium chlorate (NaCl0 3 ) and 8% by weight hydrogen peroxide (H 2 O 2 ); and 2) Sulfuric acid (78% by weight). These two preparation substances are used to genera te the active substance (chlorine-free chlorine dioxide) onboard and are not themselves ac tive substances.

Purate ® is discussed in more detail in Section 2.0.1.1 and sulfuric acid is discussed further in Section 2.0.1.2 below.

Active Substance: Chlorine-free chlorine dioxide is the active subs tance that is generated onboard and has “...specific action on or against har mful aquatic organisms and pathogens” (Guideline 9, 2.1.1). Additional information regar ding chlorine dioxide is presented in Section 2.0.2.1 below.

Relevant Chemicals: Ecochlor discusses the following two substances a s Relevant Chemicals in Section 2.0.3: 1) Sulfate ion (as sodium sulfate or sulfuric acid); a nd

2) Chlorite ion (as sodium chlorite). Based on the G9 definition of relevant chemicals, b oth of these substances are “...transformation or reaction products that are produced during the t reatment process...” (Guideline 9, 2.1.4).

Sulfate ions are discussed as a relevant chemical b ecause a slight excess of sulfuric acid is used during the chlorine dioxide generation process. Th is is done to ensure high chlorine dioxide production efficiency. As such, additional sulfate ions (19 mg/L) may be added to ballast water treated with chlorine dioxide. Although the additi on of sulfate ions to sea water as a result of treatment with the Ecochlor ® BWTS is inconsequential, Ecochlor presents justifi cations to fully explain the chemistry associated with the treatment process. Section 2.0.3.1 of the application provides further information regarding sulfate ions that clearly demonstrates that sulfate ions are not added to treated ballast water at environmental ly relevant concentrations.

As the primary reaction by-product in ballast water after disinfection with chlorine-free chlorine dioxide, Ecochlor classifies chlorite ion (ClO 2 - ), or sodium chlorite (NaClO 2 ) as a relevant chemical. Detailed information on chlorite ion is presented in Section 2.0.3.2 below.4

Chemical analysis and known chemical principles of disinfection using chlorine dioxide that is generated in the chlorine-free method used with the Ecochlor ® BWTS indicate that no other reaction by-products are present at environmentally relevant concentrations. However, biocide treatment of water can raise questions regarding th e formation of THM’s and/or HAA’s. Chemical data and justifications regarding these su bstances are located in Sections 1.0.1 (above) and 2.0.3.3.

Table T2.1 below provides an overview of the chemic als involved in the Ecochlor ® BWTS and descriptions of each chemical follow the table.

Table T2.1 – Overview of Chemical Identification
Ingredient (IUPAC Name) Identification Numbers Chemical

Formula Structural

Formula Molecular

Weight Percentage

(by weight) Applied

Concentration Preparation Chemicals

1. Purate ® a. Hydrogen Peroxide b. Sodium Chlorate a. CAS # 7722-84-1

b. CAS # 7775-09-9 a. H 2 O 2 b. NaClO 3 a.

b. a. 34.01

b. 106.44 a. <8%

b. 40% a. 0.05-2.9 M

b. 0.5-3.2 M

2. Sulfuric Acid CAS# 7664-93-9 H 2 SO 4 98.08 78% 0.75-4M

Active Substance in Ballast Water

Chlorine dioxide CAS# 10049-04-4 ClO 2 67.45 -- < 5 mg/L in ballast water Relevant Chemicals in Ballast Water

1. Sulfate ion (as sodium sulfate or sulfuric acid) CAS # 7757-82-6

or CAS# 7664-93-9 Na 2 SO 4 or H 2 SO 4 or 142.04

or

98.08 By-product < 20 mg/L

2. Sodium Chlorite (present as chlorite ion) CAS # 7758-19-2 NaClO 2 90.45 By-product < 5 mg/L

2.0.1 Preparations In order to generate chlorine dioxide onboard Ecoch lor ® is utilizing a two precursor chemical approach. The two preparation chemicals, Purate ® and sulfuric acid, are mixed under controlled conditions to generate chlorine dioxide, which is t hen injected into the ballast water stream. The preparation chemicals are not added to the ballast water directly, and are not the active substance.5

2.0.1.1 Purate ®

Purate ® is a proprietary formulation from Eka Chemicals co ntaining 40% by weight sodium chlorate (NaCl0 3 ) and 8% by weight hydrogen peroxide (H 2 O 2 ). Therefore, the Ecochlor ® BWTS utilizes chlorate-based chlorine dioxide gener ation technology. For comparison purposes only, the USEPA specifies that chlorate ion generat ors used in drinking water applications operate at 95% efficiency. This means that at a mi nimum, 95% of the sodium chlorate in Purate ® is converted to chlorine dioxide. Efficiency is th e amount of chlorine dioxide formed, divided by the sum of all possible oxychlorine comp ounds that could form. Hydrogen peroxide is not a part of the efficiency calculation.

100 x ] ClO [ + ] ClO [ + ] ClO [ O H ]

ClO [

= Efficiency

3 2 2 2 2 2

− − + ] [ %

Although the Ecochlor ® BWTS is not treating drinking water, the system’s chlorine dioxide generator is operated to achieve a minimum 95% effi ciency. This high efficiency reduces the potential for the preparation chemicals to be prese nt as residual substances in treated ballast water. The individual components of Purate ® (hydrogen peroxide and sodium chlorate) are discussed in more detail below to explain why they are not considered relevant residual chemicals.

It should also be recognized that the Purate ® solution acts as a precursor to the active substan ce and is consumed during chlorine dioxide generation. It is not the active substance itself. Therefore, Ecochlor is not submitting comprehensive toxicity data for the Purate ® chemicals in this application as it is not relevant to an evalua tion of treated ballast water. However, data on the individual components of Purate ® (hydrogen peroxide and sodium chlorate) are provid ed where pertinent to human health and/or ship safety.
Hydrogen Peroxide:
The presence of hydrogen peroxide in the Purate ® solution is designed to chemically reduce chlorate ion (+5 oxidation state) to chlorine dioxi de (+4 oxidation state). Thus, it is reasonable to presume that a slight stoichiometric excess of h ydrogen peroxide may be present in the chlorine dioxide solution. This being the case, it is important to understand what happens to any excess hydrogen peroxide that may be present in the chlorine dioxide solution generated by the Ecochlor ® BWTS.

Chlorine dioxide reacts with hydrogen peroxide in a cidic solution to slowly form chloride ion. In basic solution, chlorine dioxide reacts rapidly (minutes time scale) with hydrogen peroxide to form chlorite ion. Thus, any excess hydrogen perox ide that might be present in the acidic mixing chamber (where chlorine dioxide generation occurs i n the Ecochlor ® BWTS) is likely to react with chlorine dioxide and form chloride ion, which is ubiquitous in the marine environment. Alternatively, if any excess hydrogen peroxide were to be carried over into the ballast water which is slightly basic, it will react with chlorin e dioxide to form chlorite ion. Ultimately, the eventual fate of any residual hydrogen peroxide fro m Purate ® is to form oxygen and water, and its reducing effect on chlorine dioxide is to form either chloride ion or chlorite ion.6

Purate ® contains 8% hydrogen peroxide. At a chlorine diox ide treatment dose of 5.0 mg/L, the maximum initial concentration of hydrogen peroxide in the chlorine dioxide solution at 95% reaction efficiency is 0.35 mg/L. As discussed abo ve, this low level residual will react with chlorine dioxide to form either chloride ion or chl orite ion and will not persist in treated ballast water. As such, Ecochlor does not consider hydroge n peroxide a relevant chemical applicable to an evaluation of the Ecochlor ® BWTS.

Sodium Chlorate: Although the major degradation by-product of disinf ection with chlorine-free chlorine dioxide is chlorite ion, some chlorate ion can also be produce d. However, residual chlorate ion from the chlorine dioxide generation process is expected in low concentrations due to the small excess sulfuric acid applied to the Purate ® solution during the chlorine dioxide generation pr ocess. As mentioned above, the chlorine dioxide generator is operated at a minimum 95% efficiency to ensure complete conversion of sodium chlorate and e fficient chlorine dioxide generation.

Based on a 5.0 mg/L applied dose of chlorine dioxid e, a calculated chlorate ion concentration on the order of 0.2 to 0.49 mg/L may be present in the treated ballast water. These concentrations of chlorate ion in treated ballast water have been confirmed by ion chromatographic analysis (See Figures F2.1 through F2.3, Tables T2.2 through T2.4, T2.8). Again, for comparison purposes, these concentrations of chlorate ion are well within the reported range of chlorate ion measured in drinking water systems (United States) that use chlorine dioxide to treat water for human consumption. Because there is no US standard for chlorate ion in drinking water and the fact that the measured chlorate ion concentration i s within the range presented in USEPA published documents for drinking water, Ecochlor do es not consider it a chemical of concern in treated ballast water. Therefore, Ecochlor does no t consider chlorate ion a relevant chemical applicable to an evaluation of the Ecochlor ® BWTS.

2.0.1.2 Sulfuric Acid
The sulfuric acid (H 2 S0 4 ) used to generate chlorine-free chlorine dioxide i s industrial grade 78% by weight. A slight excess of sulfuric acid is add ed to Purate ® to increase the efficiency of the chlorine dioxide generation reaction. Thus, a low concentration of sulfuric acid remains (as sulfate ion) after the generation of chlorine dioxi de and can be measured in treated ballast water. As such, Ecochlor further discusses sulfuric acid b elow in Section 2.0.3, Relevant Chemicals. Analytical data (sulfate ion concentration and pH) from treated ballast water is presented in Table T2.8 of Section 2.0.3.3.

2.0.2 Active Substance
2.0.2.1 Chlorine Dioxide The active substance generated by the reaction of t he two precursor chemicals is chlorine-free chlorine dioxide (ClO 2 ). Chlorine dioxide is generated on demand and imm ediately injected into the ballast water based on the amount of ballast wa ter being pumped onboard. The preparation chemicals are not added to the ballast water direct ly. Chlorine dioxide treatment occurs only during uptake of ballast water. Chlorine dioxide i s not stored onboard as a concentrated chemical at any time.7

When used to treat ballast water, chlorine dioxide will rapidly react (oxidize / disinfect) with susceptible organisms and certain chemical componen ts over time. This continuing consumption of chlorine dioxide is described as the chlorine di oxide demand. The concept of demand is widely used in water purification to help determine the dose and contact time (C x t) needed for effective disinfection of a specific water source. In practice this means that when a 5.0 mg/L dose of chlorine dioxide is added to ballast water, there is typically a rapid decrease in the chlorine dioxide concentration followed by a contin uing reaction of the remaining chlorine dioxide until the demand of the water is met. Afte r meeting the demand, the chlorine dioxide will maintain a residual concentration and continue to react with components in the ballast water. This results in a slow decrease in concentration ov er time until the concentration of chlorine dioxide falls to a level that is undetectable by av ailable analytical methods.

In the significant number of tests Ecochlor has con ducted, ballast water treated with 5.0 mg/L chlorine dioxide has a typical decay of less than 2 4 hours. The chlorine dioxide demand/decay of a specific water sample will vary depending on f actors such as water temperature and amount of organic matter present. To isolate the effect o f temperature on chlorine dioxide demand, testing was performed in a laboratory setting where temperature was controlled. A whole water sample from Newark, New Jersey was sent to NovaChem Laboratories for testing. Figures F2.1, F2.2, and F2.3 show the chlorine dioxide demand of the New Jersey water at 4°C, 12°C and 24°C, respectively. Data Tables T2.2, T2.3 and T2. 4 correspond to these demand study curves.

Figure F2.1 – Example of Chlorine Dioxide Demand Cu rve, 4°C

Note: Demand testing on raw water samples perfo rmed by NovaChem Laboratories8 Table T2.2 – Ecochlor Chlorine Dioxide Demand Study , 4oC

Ecochlor Ballast Water Chlorine Dioxide Decay Study

Source Water New Jersey Ballast Water ClO2 Dose 5.06 mg/L Water Temp 4 oC

Time after ClO 2 treatment (minutes) Chlorine

Dioxide ClO 2 (mg/L) Chlorite Ion

ClO 2 - (mg/L) Chlorate Ion

ClO 3 - (mg/L) 0 5.06 ND ND
5 3.50 0.742 0.001 30 2.80 0.855 0.055 60 1.90 1.285 0.110
180 1.40 1.727 0.169 300 1.10 -- --
480 0.21 -- --
660 0.00 1.796 0.282 Note: Demand testing on raw water samples performe d by NovaChem Laboratories ND = not detected, “--“ = not measured
Figure F2.2 – Example of Chlorine Dioxide Demand Cu rve, 12°C

Note: Demand testing on raw water samples perfo rmed by NovaChem Laboratories9 Table T2.3 – Ecochlor Chlorine Dioxide Demand Study , 12oC

Ecochlor Ballast Water Chlorine Dioxide Decay Study

Source Water New Jersey Ballast Water ClO2 Dose 5.01 mg/L Water Temp 12 oC

Time after ClO 2 treatment (minutes) Chlorine Dioxide

ClO 2 (mg/L) Chlorite Ion

ClO 2 - (mg/L) Chlorate Ion

ClO 3 - (mg/L) 0 5.01 ND ND 5 3.30 0.747 0.046 30 2.30 1.105 0.161 60 1.30 1.520 0.184 120 0.71 2.200 -- 180 0.43 2.203 -- 240 0.20 2.075 0.265 300 0.12 1.912 -- 360 0.02 1.902 0.285 Note: Demand testing on raw water samples performed by NovaChem Laboratories ND = not detected, “--“ = not measured
Figure F2.3 – Example of Chlorine Dioxide Demand Cu rve, 24°C

Note: Demand testing on raw water samples perfor med by NovaChem Laboratories10 Table T2.4 – Ecochlor Chlorine Dioxide Demand Study , 24oC

Ecochlor Ballast Water Chlorine Dioxide Decay Study

Source Water New Jersey Ballast Water ClO2 Dose 5.05 mg/L Water Temp 24 oC

Time after ClO 2 treatment (minutes) Chlorine Dioxide

ClO 2 (mg/L) Chlorite Ion

ClO 2 - (mg/L) Chlorate Ion

ClO 3 - (mg/L) 0 5.05 ND ND 5 -- 1.225 0.110 15 2.20 1.533 0.140 30 1.52 1.956 0.178 50 0.83 --` 0.236 60 0.73 2.229 0.227 120 0.19 2.351 0.245 150 0.04 2.369 0.243 Note: Demand testing on raw water sample s performed by NovaChem Laboratories ND = not detected, “--“ = not measured
As the figures depict, the chlorine dioxide demand / decay proceeds as anticipated with an initial rapid decrease in chlorine dioxide concentration un til the demand of the water is met, and then a residual concentration decays over time. The figur es also demonstrate that the chlorine dioxide decay rate can decrease in colder water and increas e in warmer water.

Because of the known decay behavior and chemical pr operties, it is unlikely that chlorine dioxide will be present in treated ballast water at the time of discharge. Additionally, the Ecochlor ® BWTS employs a methodology that treats ballast wat er during uptake rather than prior to discharge, which further ensures sufficien t holding time to reach undetectable levels of chlorine dioxide. Although unlikely, Ecochlor reco gnizes that there is potential for the discharge of treated ballast water containing minimal amounts of chlorine dioxide. In light of this, chlorine dioxide toxicity data is presented in this applicat ion for review. It should also be noted that one could reasonably anticipate that any discharged chl orine dioxide would quickly react (decay) upon introduction to the receiving water.

2.0.3 Relevant Chemicals

2.0.3.1 Sulfate Ion and Sulfuric Acid
During the generation of chlorine-free chlorine dio xide, conversion of sodium chlorate to chlorine dioxide involves the use of sulfuric acid. To ensure high chlorine dioxide production efficiency, an excess of acid is typically added to the Purate ® solution. Thus, the applied chlorine dioxide solution is slightly acidic and su lfate ion (SO 4 2- ), as sulfuric acid or sodium sulfate, is produced as a by-product.
The stoichiometric equation for the chlorine dioxid e generation process is:

2ClO 3 - + 2H 2 O 2 + 2H 2 SO 4 → 2ClO 2 + O 2 + SO 4 -2 + 2H 2 O
In water, sulfuric acid is totally miscible and rea dily dissociates to form hydrogen ion (H + ) and sulfate ions (SO 4 2- ). The reaction stoichiometry indicates that for e very mole of chlorine dioxide produced, 0.5 moles of sulfate ion is produced. Th us, if 5.0 mg/L ClO 2 is added to the ballast11

water it is accompanied by less than 4.0 mg/L SO 4 2- . Further, due to the slight excess of acid needed for reaction efficiency, at a chlorine dioxi de dose of 5.0 mg/L a maximum of 15.0 mg/L additional sulfate ion might be added to the ballas t water. Thus, a maximum total of 19.0 mg/L of sulfate ion may be added along with a small amou nt of acidity. This added acidity is easily buffered by the dissolved carbon dioxide (CO 2 ) naturally present in seawater. Analysis of treated ballast water shows that the effect of the excess sulfuric acid on pH is nominal. Table T2.8 presents that control tank ballast water had a pH of 7.6, and chlorine dioxide treated ballast water had a pH of 7.3.
Because sulfate ion is one the major ions naturally present in seawater, the addition of sulfate ion from the BWTS is not considered environmentally rel evant. Chemical analysis of treated ballast water from the San Francisco Bay area (Richmond, CA ) confirms this statement. Table T2.8 below presents analytical data in which the sulfate ion concentration in the control ballast tank (no chlorine dioxide treatment) was 1,902 mg/L, whi le the chlorine dioxide treated ballast tank had a sulfate ion concentration of 1,826 mg/L (meas ured 8 days after treatment). These numbers support the theoretical conclusion that sulfate ion will not be added to treated ballast water at environmentally relevant concentrations.
Further, at environmentally relevant concentrations , sulfuric acid is completely dissociated and sulfate ion is at or below natural levels. Complet e ionization also implies that sulfuric acid itself will not adsorb on particulate matter and will not accumulate in living tissues 1 . Therefore, the known chemical properties of sulfuric acid, along w ith the chemical analysis of treated ballast water, provide justification that it will not be of concern to the aquatic environment or humans when discharged in treated ballast water. As such, aquatic toxicity data for sulfate ions is not presented in this application. However, data on sul furic acid is provided where pertinent to human health and/or ship safety.

2.0.3.2 Chlorite Ion
Based on the above discussion, the primary reaction by-product in the ballast water after disinfection and/or decay of chlorine dioxide is ch lorite ion (ClO 2 - ), or sodium chlorite (NaClO 2 ). When chlorine dioxide reacts it loses an electr on and forms chlorite ion, which is also a low level biocide.

ClO 2 → ClO 2 - + e The concentration of chlorite ion at the time of ba llast water discharge will vary depending upon the source of the ballast water, the treatment dose , and the hold time in the ballast tanks. In water, chlorite ion decomposes to chloride ion. Li ght, microorganisms, enzymes, and metals (such as iron) in the water contribute to the decom position of chlorite ion. Thus, in a way similar to chlorine dioxide, chlorite ion will in many case s have an observable demand. Over time the chlorite ion concentration decreases through contin uing reactions with humic or other labile substances in the ballast water, resulting in an in crease of chloride ion (Cl - ).

In addition to the chlorite ion data presented in S ection 2.0.2.1 above, the chlorite ion demand of water from Newark, New Jersey was determined and th e observed curve is depicted in Figure F2.4.

1 OECD SIDS SIAR, SIAM 11 (January 2001), UNEP Publi cations.12 Figure F2.4 – Example of Chlorite Ion Demand Curve Newark, NJ Water

Ballast Water Chlorite Ion Demand

1.94 mg/L, 20 C

0.00 0.50 1.00 1.50 2.00 2.50

0 10 20 30 40 50 60 70 80
Time (Hr)Concentration (mg/L)

Note: Demand testing on raw water samples per formed by NovaChem Laboratories Table T2.5 – Ecochlor Chlorite Ion Demand Study, 20 oC

Ecochlor Ballast Water Chlorite Ion Demand Study

Source Water New Jersey Ballast Water Chlorite Dose 1.94 mg/L Water Temp 20 oC

Time after ClO 2 - treatment (hour) Chlorite Ion ClO 2 - (mg/L) 0 1.94 1 0.88 18 0.30 42 0.36 69 0.19 Note: Demand testing on raw water samples performed by NovaChem Laboratories It is important to note that the above figure and d ata table depicts a laboratory setting where the water sample is static. Once the demand of the wat er has been met, the chlorite ion concentration becomes stable in the closed system. However, in an actual onboard chlorine dioxide treatment scenario the treated ballast wate r will be discharged. Once the ballast water is discharged, two forces act on the remaining chlorit e ion. The first is the dilution of the ballast water with the receiving water and the second is th e chlorite demand of the receiving water.

Because the chlorite ion reaction by-product may pe rsist in chlorine dioxide treated ballast water at the time of discharge, chlorite toxicity data is presented in this application for review. However, Ecochlor does not believe that the low con centration of chlorite ion that may be present in treated ballast water poses unacceptable risks. Additionally, any chlorite ion present at the time treated ballast water is discharged into t he marine environment will continue to decrease in concentration based on the chlorite ion demand d iscussed above and dilution effects upon discharge. Toxicological data verifying that treat ed ballast water that may contain low levels of chlorite ion does not present unacceptable risks ar e presented in Sections 5.1 and 5.2.13

2.0.3.3 Trihalomethanes and Haloacetic Acid By-Products

The Ecochlor ® BWTS generates chlorine-free chlorine dioxide usin g the Eka Chemicals Purate ® technology, a patent-protected chlorine dioxide gen eration method. Eka’s Purate ® technology is a chlorate-based chlorine dioxide generation proces s. This method differs from other conventional chlorine dioxide generation methods th at involve use of aqueous or gaseous chlorine, making the chlorine-free Purate ® method environmentally superior. Additionally, Eka’s Purate ® technology produces chlorine dioxide efficiently, thereby controlling the required input of precursor chemicals and eliminating produc tion of unwanted by-products.
To further explain the chemistry, chlorine dioxide can be generated using differing methods, and a number of chlorate ion reduction processes exist to produce chlorine dioxide. Some of these methods can also produce chlorine as a generation i ntermediate or by-product (e.g., Mathieson, Solvay, R2 and R3/SVP processes). To avoid the chl orine by-product in these traditional methods, a new process was developed where hydrogen peroxide is the reducing agent and hydrochloric acid is replaced by sulfuric acid. Th is newer process, utilized in the patentprotected Eka Chemicals Purate ® technology employed with the Ecochlor ® Ballast Water Treatment System (BWTS), does not involve or create free available chlorine (FAC).

Additionally, it is important to note that chlorine dioxide and chlorine act very different chemically. For instance, chlorine dioxide is an o xidant, yet it does not chlorinate. In contrast, FAC is both an oxidant and a chlorinating agent. C hlorine dioxide disinfection is the result of a 1e- transfer mechanism resulting in the formation o f chlorite ion (ClO 2 - )

ClO 2 → ClO 2 - + e Because FAC is not present in any detectable concen tration, the application of chlorine-free chlorine dioxide results in oxidation without the f ormation of organic by-products such as THM’s, and other unwanted by-products such as HAA’s are minimized.

Chemical analysis of ballast water treated with chl orine-free chlorine dioxide presented in Table T2.8 confirms that THM’s are not directly formed an d that HAA’s are not present at environmentally relevant concentrations. The data show that, similar to the untreated ballast water (control), FAC is not measurable (<0.05 m/L) (EPA Standard Method 4500-Cl F, DPD) in treated ballast water when measured on Day 3 follow ing treatment. Further, a chlorine dioxide residual is not observed (Palintest Lissamine Green -B method), indicating that the entire 5.0 mg/L dose of chlorine dioxide has been reacted.

The data in Table T2.8 shows no formation of THM’s (<1 μg/L) after treatment of ballast water with chlorine dioxide from the Ecochlor ® BWTS. The table also shows the low level (12 μg/L ) presence of a single haloacetic acid (dibromoacetic acid (DBAA)). These data are consistent with chemistry of chlorine dioxide as an oxidant. The drinking water standard in the United States is <80 μg/L total THM’s and <60 μg/L total H AA. Both of these standard levels are achieved in the ballast water treated with chlorine -free chlorine dioxide. Based on the chemical analysis and the G9 definition of relevant chemical s under 2.1.4 of the Guideline, Ecochlor does not consider THM’s or HAA’s as relevant chemicals o r applicable to an evaluation of the Ecochlor ® BWTS.14

Table T2.8 – Analysis of Ballast Water Treated Onbo ard the M/V Moku Pahu
,

San Francisco Bay Area (Richmond, CA)

Parameter Control Ballast Water Ballast Water

Treated Onboard + 3 Day 13 Feb 2008 Ballast Water

Treated Onboard + 5 Day 15 Feb 2008 pH 7.6 7.3 7.3 FAC <0.05 mg/L <0.05 mg/L -- ClO 2 -- <0.05 mg/L <0.05 mg/L ClO 2 - <0.05 mg/L 0.91 mg/L 0.24 mg/L ClO 3 - <0.10 mg/L 0.49 mg/L 0.49 mg/L Br - 50 mg/L -- -- BrO 3 - <0.02 mg/L -- <0.02 mg/L (+11 Day) SO 4 - 2 1902 mg/L -- 1826 mg/L (+ Day 8) THM’s Bromdichloromethane Bromoform Chloroform Dibromochloromethane <1 μg/L <1 μg/L <1 μg/L <1 μg/L -- <1 μg/L <1 μg/L <1 μg/L <1 μg/L

HAA’s Dibromoacetic Acid Dichloroacetic Acid Bromoacetic Acid Monochloroacetic Acid Trichloroacetic Acid <1 μg/L <1 μg/L <1 μg/L <1 μg/L <1 μg/L -- 12 μg/L <1 μg/L <1 μg/L <1 μg/L <1 μg/L Note: Demand testing on raw water sample s performed by NovaChem Laboratories “--“ = not measured

2.1 DATA ON EFFECTS ON AQUATIC PLANTS, INVERTEBRATE S AND FISH, AND OTHER BIOTA, INCLUDING SENSITIVE AND REPRESENTA TIVE ORGANISMS (G9: 4.2.1.1) The toxicology data presented in this application v aries by topic and is selective by design. To clarify, the toxicology data set required by Guidel ine 9 involves several categories; 1) aquatic toxicity, 2) mammalian toxicity and 3) environmenta l fate and effect. It is Ecochlor’s opinion that these categories relate to the Ecochlor proces s at different phases of treatment and potential exposure to the substances associated with the Ecoc hlor ® BWTS is not the same for each category. As such, each toxicological category was evaluated to determine where a potential exposure existed and what chemicals were of potenti al concern throughout the treatment process.

For example, the acute and chronic aquatic toxicitydata submitted is intended to provide a reallife scenario of what chemicals may be present when treated ballast water is discharged. Because Purate ® and sulfuric acid are converted into chlorine-free chlorine dioxide and are not present at significant concentrations in treated ba llast water, aquatic toxicity data is not provided for these chemicals. However, because treated ball ast water may contain chlorine dioxide (this should not happen if the system is used as directed ) and chlorite ion (the primary by-product of disinfection with chlorine dioxide), aquatic toxici ty data is provided for these chemicals.

Similarly, because Purate ® and sulfuric acid are stored onboard and a potenti al for human exposure (crew or technicians) exists, mammalian to xicity data is provided for these chemicals. However, because treated ballast water is not typic ally handled by crew or technicians, Ecochlor15

did not provide mammalian toxicity data on chlorite ion as this does not seem relevant. Even in a situation where human contact with treated ballas t water could occur, (i.e. water sample collection) the chemicals that may be present have been determined analytically to be at concentrations that are not of concern to humans.

Toxicity testing with THM’s and HAA’s was not consi dered because chemical analysis of treated ballast water indicates that these substanc es are not relevant to an evaluation of ballast water disinfected with chlorine-free chlorine dioxi de (see also Sections 1.0.1, 2.0.3.3 and 5.3). Additionally, whole effluent testing of the treated ballast water includes the sum of all substances formed in the treatment process. In Ecochlor’s opi nion, aquatic toxicity testing on treated ballast water reflects the most accurate information on the potential toxicological effects of the treated water a ship will discharge. Toxicity testing on t he precursor chemicals and/or intermediate substances is informative, but may not reflect the most realistic toxicological evaluation of treated ballast water.

Toxicity tests for chlorine dioxide were performed by Nautilus Environmental and end-points are based on measured concentrations of chlorine dioxid e at the start of the exposure periods. Acute toxicity tests were static and chronic tests were s tatic renewal with a daily renewal of test solutions, with the exception of tests with Macrocystis pyrifera, Mytilus sp. and Skeletonema

costatum , which were static, and the 96 hr test with Clupea pallasi in which the solution was renewed only after 48 hr of exposure. All tests we re conducted according to USEPA guidelines for conducting short term acute and chronic toxicit y tests (USEPA 1995, 2002), with the exception of the tests with Skeletonema costatum , which followed ASTM (1998) methodology, and tests with Clupea pallasi , which were based on methodology developed by Dr. Paul Dinnel from the Shannon Point Marine Center.

Toxicity tests for chlorite were static, with the e xception of 7 day tests with Mysidposis bahia and Atherinops affinis , which were static renewal, with daily renewal of solutions. All tests were conducted according to USEPA guidelines for conduct ing short term acute and chronic toxicity tests (USEPA 1995, 2002).

According to 3.2.1.2 of the Draft Methodology (MEPC 55/2/16, Annex 4), “In the case of whole effluent testing, EPA, or equivalent, short term me thods for estimating the acute toxicity of substances and discharge provide acceptable alterna tives.”

2.1.1 Acute Aquatic Toxicity
2.1.1.1 Chlorine Dioxide Acute toxicity data (LC50 or EC50) are presented in Table T2.9 for survival of the crustacean Mysidposis bahia and the larval fish Menidia beryllina (inland silverside), as well as spore germination of the giant kelp ( Macrocystis pyrifera ). EC50 values for these species were ~0.4, >0.4 and 0.2 mg/L, respectively. Additional data a re presented for survival of a second fish, the Pacific herring ( Clupea pallasi ).

2.1.1.2 Chlorite Ion Acute toxicity data (LC50 or EC50) are presented in Table T2.9 for survival of the crustacean Mysidopsis bahia and the larval fish Cyprinidon variegatus (sheepshead minnow), as well as16

spore germination of the giant kelp ( Macrocystis pyrifera ). EC50 values for these species were 0.58, 75.0 and >15.4 mg/L, respectively.

2.1.1.3 Treated Ballast Water Acute toxicity data (LC50 or EC50) are presented in Table T2.9 for survival of the crustacean Mysidopsis bahia in ballast water treated with chlorine-free chlorin e dioxide. EC50 values for these species were 38.7% and 37.7%.

Table T2.9 – Overview of Acute Aquatic Toxicity

Test Substance F

C A Species Test Type EC50 mg/L NOEC

mg/L Reference/

comments

Preparations

1. Purate ® -- -- -- -- See Section 2.0.1.1 for justification of not providing data

2. Sulfuric Acid -- -- -- -- See Section 2.0.3.1 for justification of not providing data Active Substance

Chlorine Dioxide F Menidia beryllina 96 hr survival a >0.4 0.4 Nautilus Env. 2005

F Clupea pallasi 96 hr survival 0.35 0.22 Nautilus Env. 2005
C Mysidopsis bahia 48 hr survival a ~ 0.4 0.04 b Nautilus Env. 2005

A Macrocystis pyrifera 48 hr germination 0.20 0.14 Nautilus Env. 2006
Relevant Chemicals

1. Sulfate Ion/ Sulfuric Acid -- -- -- -- See Section 2.0.3 for justification of not providing data

2. Chlorite Ion (Sodium chlorite) F Cyprinidon variegatus 96 hr survival 75.0 13.9 Env. Sci. Eng. 1994b

C Mysidopsis bahia

96 hr survival 0.58 NR Env. Sci. Eng. 1994a

A Macrocystis pyrifera 48 hr germ. >15.4 15.4 Nautilus Env. 2007
Treated Ballast Water

5.0 mg/L dose of ClO 2 C Mysidopsis bahia 48 hr survival 38.7% 25% Nautilus Env. 2006

C Mysidopsis bahia

48 hr survival 37.7% 25% Nautilus Env. 2006
F = Fish, C = Crustacean, A = Algae, NR = Not Repor ted

a Calculated on the basis of data from the chronic t oxicity test with this species.
b Reported NOEC is highly conservative because the n ext concentration tested was 10-times higher (see d iscussion in Section 2.1.2.1).

2.1.2 Chronic Aquatic Toxicity
2.1.2.1 Chlorine Dioxide Chronic toxicity data in Table T2.10 include data f or a fish (survival and growth of larval Menidia beryllina ), an invertebrate (survival and growth of a mysid, Mysidopsis bahia ) and an algae (germination and growth of giant [ Macrocystis pyrifera ] kelp spores), as well as for two additional species (larval development for a mollus c [ Mytilus sp .] and population growth for a diatom [ Skeletonema costatum ]). The most sensitive test species was Mytilus sp. , which exhibited a chronic NOEC of 0.09 mg/L and an EC50 o f 0.22 mg/L on the basis of a larval development test.17

It should be noted that the chlorine dioxide NOEC o f 0.04 mg/L reported in Table T2.10 for Mysidopsis bahia is likely overly conservative and resulted from th e ten-fold dilution series employed in this test. A partial effect was observ ed at 0.4 mg/L chlorine dioxide with this species, and no effect at the next lower concentrat ion of 0.04 mg/L. Based on acute tests, the bivalve larval development test using Mytilus sp . was clearly more sensitive than M. bahia and, consequently, a definitive test was conducted using the bivalve larval development test with a narrower (two-fold) dilution series. Thus, althoug h the NOEC reported for Mytilus sp . of 0.09 mg/L appears to be higher than the NOEC for M. bahia , this is largely an artifact associated with the concentrations which were tested. Consequently , it is appropriate to consider the test using Mytilus sp . to be the most sensitive test, and therefore the most sensitive NOEC should be the one reported for this test (0.09 mg/L).

2.1.2.2 Chlorite Ion Table T2.10 includes chronic toxicity data for a fi sh (survival and growth of larval topsmelt, Atherinops affinis ), an invertebrate (survival and growth of a mysid, Mysidopsis bahia ) and an alga (germination and growth of giant kelp [ Macrocystis pyrifera ] spores), as well as for two additional species (larval development for a mollus c, Crassostria virginica and an echinoderm, Strongylocentrotus purpuratus ). The most sensitive test species was Mysidopsis bahia , which exhibited a chronic NOEC of 0.18 mg/L and an EC50 o f 0.25 mg/L on the basis of a 7-day survival and growth test.

2.1.2.3 Chlorine Dioxide Chronic toxicity testing on the mollusk Mytilus sp. was performed on ballast water disinfected with chlorine-free chlorine dioxide. An EC50 of >8 1% and 84% was exhibited. Chronic NOEC values of 11.7% and 12% for the crustacean Mysidopsis bahia were calculated based on the acute toxicity results.

Table T2.10 – Overview of Chronic Aquatic Toxicity

Test Substance F

C A M Species Test Type EC50 mg/L NOEC

mg/L Reference/

comments

Preparations

1. Purate ® -- -- -- -- See Section 2.0.1.1 for justification of not providing data

2. Sulfuric Acid -- -- -- -- See Section 2.0.3.1 for justification of not providing data Active Substance

Chlorine Dioxide F Menidia beryllina 7 day surv/growth >0.4 0.4 Nautilus Env. 2005

F Clupea pallasi 18 day embryo devpt >0.33 0.33 Nautilus Env. 2005

C Mysidopsis bahia 7 day surv/growth ~ 0.4 0.04 a Nautilus Env. 2005

A Macrocystis pyrifera 48 hr germination 0.20 0.14 Nautilus Env. 2006

D Skeletonema costatum 96 hr growth 3.09 2.09 Nautilus Env. 2006

M Mytilus edulis 48 hr development 0.22 0.09 Nautilus Env. 200518 Test Substance F

C A M Species Test Type EC50 mg/L NOEC

mg/L Reference/

comments

Relevant Chemicals

1. Sulfate Ion/ Sulfuric Acid -- -- -- -- See Section 2.0.3.1 for justification of not providing data

2. Chlorite Ion (Sodium chlorite) F Atherinops affinis 7 day surv/growth >13.8 6.9 Nautilus Env. 2007

C Mysidopsis bahia 7 day surv/growth 0.25 0.18 Nautilus Env. 2007

A Macrocystis pyrifera 48 hr germ. >15.4 15.4 Nautilus Env. 2007

E Strongylocentrotus purpuratus Development 10.4 5.0 Nautilus Env. 2007

M Crassostrea virginica Development 21.4 14.3 Env. Sci. Eng. 1994c Treated Ballast Water

5.0 mg/L dose of ClO 2 M Mytilus sp. Development >81% 81% Nautilus Env. 2006

M Mytilus sp. Development >84% 84% Nautilus Env. 2006

C Mysidopsis bahia

48 hr survival -- 12% b Nautilus Env. 2006

C Mysidopsis bahia

48 hr survival -- 11.7% b Nautilus Env. 2006 F = Fish, C = Crustacean, A = Algae, D = Diatom, M = Mollusk, E = Echinoderm

a Reported NOEC is highly conservative because the n ext concentration (NOEC) tested was 10-times higher

. b Chronic NOEC calculated using acute-to-chronic rat io of 3.22

2.1.3 Endocrine Disruption There is no evidence to suggest that Purate ® or sulfuric acid would result in endocrine disrupt ion. There is no evidence to suggest that chlorine dioxi de or chlorite would result in endocrine disruption 2

. 2.1.4 Sediment Toxicity 2.1.4.1 Preparations The sodium chlorate and hydrogen peroxide component s of Purate ® are both non-organic and soluble in water. The chemical properties of both components indicate that they would not be expected to accumulate in sediments.

2.1.4.2 Active Substance Chlorine dioxide is not persistent as a result of i ts rapid degradation pathway to chlorite, and is not expected to bioaccumulate since it is non-organ ic and does not have hydrophobic or lipophilic properties. This chemical would not be expected to accumulate in sediments 2

.

2.1.4.3 Relevant Chemicals In water, sulfuric acid is totally miscible and rea dily dissociates to form hydrogen ion (H + ) and sulfate ions (SO 4 2- ). At environmentally relevant concentrations, sul furic acid is completely dissociated and sulfate ion is at or below natural concentrations. Complete ionization also implies that sulfuric acid itself will not adsorb o n particulate matter and will not accumulate in living tissues 1

.
Chlorite ion is not persistent as a result of its d egradation pathway to chloride ion in both water and soils, and is not expected to bioaccumulate sin ce it is non-organic and does not have

2 Review of the Environmental Fate and Effects of C hlorine Dioxide and Chlorite, Nautilus Environmenta l, 2007.19

hydrophobic or lipophilic properties 2 . Therefore, chlorite would not be expected to acc umulate in sediments.

2.1.4.4 Treated Ballast Water The potential substances present in treated ballast water at the time of discharge are chlorine dioxide and chlorite ion. The capability of these constituents to accumulate in sediments is discussed above.

2.1.5 Bioavailability/Biomagnification/Bioconcentra tion and Food Web/Population Effects The active substance and relevant chemical (chlorin e dioxide and chlorite, respectively) are the only constituents potentially present in treated ba llast water that will be discharged to the environment. Both substances are highly water solu ble and are not organic in nature. Neither of these chemicals would be expected to exhibit biomag nification or bioconcentration, and consequently, would not be expected to persist in t he food web 2

.
2.2 DATA ON MAMMALIAN TOXICITY (G9: 4.2.1.2)

Test reports used in this application were from a v ariety of sources, including, but not limited to, OECD SIDS, Eka Chemicals (performed by independent laboratories), independent research, USEPA, and the National Toxicology Program. The re ports were evaluated to ensure that the data presented was generated by accredited laborato ries using accepted standard methodologies and laboratory practices. Additional discussion on data quality is presented in Section 6.5.2. The studies and documents referenced are attached t o this application.

Potential for human exposure to Ecochlor ® BWTS chemicals are limited to Purate ® , sulfuric acid and chlorine dioxide. Chlorite ion is a low-level degradation by-product that will only be present in treated ballast water. Because treated ballast water is not handled by technicians or ship’s crew, no potential for exposure exists. Therefore, mammalian toxicity data is presented for Purate ® , sulfuric acid and chlorine dioxide in this sectio n. Section 2.1 provides additional justification for the selection of toxicity data pr esented.

The toxicity data presented in this section has bee n gathered through literature review of available data. The various forms in which the che micals have been evaluated (gas, liquid, or solid phases at differing concentrations) do not ne cessarily reflect the actual form of the substance utilized in the Ecochlor ® BWTS or the potential route of exposure. Mammalia n toxicity data is presented for informational purpos es using data previously established by others. The quality of the data used is presented in Sectio n 6.5, Assessment Report of this application.20

2.2.1 Acute Mammalian Toxicity Table T2.11 – Acute Mammalian Toxicity Data

Test Substance Exposure Route Species Value range Reference/ comments

Preparations

Purate ®

Sodium Chlorate a. Acute Oral LD50 b. Inhalation LC50 a. Rat b. Rat a. >5000 mg/kg

b. 5.6 mg/L/4hr Purate ® MSDS, Eka Chemicals
Hydrogen Peroxide (10%) a. Acute Oral LD50 b. Inhalation LC50 a. Rat b. Rat a.1500 - >5000 mg/kg

b. 122 mg/L/4hr Purate ® MSDS, Eka Chemicals

Sulfuric Acid a. Acute Oral LD50 b. Inhalation LC50 a. Rat b. Rat a. 2140 mg/kg

b. 0.375 mg/L/4hr OECD SIDS SIAR, SIAM 11 (January 2001), UNEP Publications 1 Active Substance

Chlorine Dioxide a. Acute Oral LD50 (EPA OPPTS Method 870.1100)

b. Inhalation (nose) LC50 a. Rat

b. Rat a. 292 mg/kg (males)

340 mg/kg (females)

b. 32 mg/L (90 mg/m 3 )/4hr a. USEPA RED for Chlorine Dioxide and Sodium chlorite 3

b. Schorsch (1995) cited in IPCS Chlorine Dioxide (Gas) 2002) CICADS 37. 4

2.2.2 Effects on Skin and Eye Table T2.12 – Skin, Eye and Dermal Effects

Test Substance Skin Eye Sensitization Reference/ comments

Preparations

Purate ®

Sodium Chlorate Not irritating to rabbits Mildly irritating to rabbits Not sensitizing to guinea pigs. Purate ® MSDS, Eka Chemicals

Hydrogen Peroxide At concentrations <35%, not a skin irritant Highly corrosive/ irritating at concentrations>10% Not sensitizing to guinea pigs at 6% concentration Purate ® MSDS, Eka Chemicals

Sulfuric Acid Severely irritating to contaminated tissue Severe irritant Not known to be a sensitizer Sulfuric acid

MSDS, Basic Chemical Solutions Active Substance

Chlorine Dioxide Irritant Strong irritant Not located Chlorine Dioxide MSDS, Eka Chemicals

3 USEPA Reregistration Eligibility Decision (RED) fo r Chlorine Dioxide and Sodium Chlorite (Case 4023), August 2006.

4 Concise International Chemical Assessment Document (CICADS) 37, Chlorine Dioxide (Gas), 2002.21

2.2.3 Repeated-dose Toxicity Table T2.13 – Repeated-Dose Toxicity

Test Substance Exposure Route Species Value range Reference/ comments

Preparations

Purate ®

Sodium Chlorate a. Oral, 90-day subchronic

b. Oral, 90-day subchronic a. Rodent

b. Dog a. NOAEL 100

mg/kg/day

b. NOAEL 360 mg/kg/day EKA Study 86- 3112 EPA Guideline 82-1 (1987) 5

EKA Study 86- 3114 EPA Guideline 82-1 (1987) 6

Hydrogen Peroxide (10%) a. Oral, 90-day subchronic

b. Oral, 90-day subchronic a. Rodent

b. Other mammal a. NOEL 30-56.2

mg/kg

b. Not located Ito et al. 1976 and Kawasaki et al., 1969, cited by SCCP 7

Sulfuric Acid 28 day, inhalation (nose only) Rat NOEL/NOAEL not indentified OECD SIDS SIAR, SIAM 11 (January 2001), UNEP Publications 1 Active Substance

Chlorine Dioxide a. Inhalation, 60-day

b. Oral, 90-day subchronic a. Rat

b. Rat a. LOAEL – 1 mg/L

(2.8 mg/m 3 )

b. 2-15 mg/kg in drinking water. No treatment related deaths, clinical signs or effects on hematology, clinical chemistry or organ weights. Dose-related decrease in water consumption and food consumption in high dose only. Nasal cavity was identified as the target tissue with hyperplasia, squamous metaplasia and inflammatory
responses USEPA Tox. Review of Chlorine Dioxide and Chlorite, 2000 8

Daniel, 1990, cited in IPCS Chlorine Dioxide (Gas) 2002) CICADS 37 4

5 Barrett, D.S. (1987) A Subchronic (3 Month) Oral T oxicity Study of Sodium Chlorate in the Rat via Gav age. 6 Barrett, D.S. (1987) A Subchronic (3 Month) Oral T oxicity Study in the Dog via Gavage Administration with Sodium Chlorate.

7 Scientific Committee on Consumer Products (SCCP), Opinion on Hydrogen Peroxide in Tooth Whitening Pro ducts, 2005 (SCCP/0844/04).
8 USEPA Toxicological Review of Chlorine Dioxide and Chlorite, September 200022

2.2.4 Chronic Toxicity Table T2.14 – Chronic Mammalian Toxicity

Test Substance Exposure Route Species Value range Reference/ comments

Preparations

Purate ®

Sodium Chlorate a. Oral, 2 year

b. -- a. Rodent

b. Other mammal a. NOAEL < ~5

mg/kg/day for 2 years. Thyroid hyperplasia was observed in all groups of males in an NTP 2-year cancer bioassay. Survival, water consumption, and body weights were similar to controls. No clinical findings were attributed to sodium chlorate exposure.

b. Not located National Toxicology Program (2005) Technical Report on the Toxicology and Carcinogenesis Studies of Sodium Chlorate. 9

Hydrogen Peroxide (10%) a. minimum 12 month study

b. minimum 12 month study a. Rodent

b. Other mammal a. None located

b. None located SEE PARAGRAPH BELOW TABLE

Sulfuric Acid

-- -- Long term studies have focused on portal of entry effects as systemic effects are considered unlikely. OECD SIDS SIAR, SIAM 11 (January 2001), UNEP Publications 1 Active Substance

Chlorine Dioxide a. Oral, 2-year chronic

b. minimum 12 month study a. Rat

b.Other mammal a. NOAEL: 10 mg/L

b. Not located USEPA Tox. Review of Chlorine Dioxide and Chlorite, 2000 8

Although not general toxicology studies, hydrogen p eroxide has been extensively evaluated as an aid to oral hygiene in humans. “Daily use of a ... o r a 1.5% hydrogen peroxide-containing mouth rinse for 18 months or 2 years resulted in no reported adverse effects on oral health.” 7

2.2.5 Developmental and Reproductive Toxicity The sodium chlorate component of Purate ® was not teratogenic to rats at doses up to 1,000 mg/kg-day during 6-15 days of gestation. Sufficien t data is not available for the hydrogen peroxide component of Purate ® (See Purate ® MSDS in GESAMP submission).

Hydrogen peroxide was not deemed to cause any conce rn for reproductive effects by the European Chemicals Bureau 10 . Sulfuric acid is not reported to cause teratogen ic or reproductive toxicity effects in humans (See sulfuric acid MSDS in GESAMP submission). Additionally, from the OECD SIDS Initial Assessment Report 1 :

9 NTP Technical Report on the Toxicology and Carcino genesis Studies of Sodium Chlorate in F344/N Rats a nd B6C3F1 Mice (Drinking Water Studies), 2005. NTP TR 517, NIH P ublication No. 06-4457.
10 European Chemicals Bureau (2003) Hydrogen Peroxid e Summary Risk Assessment Report. Special Publicat ion I.03.148.23 “... due to irritant/corrosive effects of H 2 SO 4 , oral and dermal routes are not appropriate for te sting toxicity to reproduction. In addition, H 2 SO 4 is a direct-acting toxicant. The acid as such, is not expected to be absorbed or distributed throughout the body. Theref ore, it is not likely that it will reach male and f emale reproductive organs following exposures by any rout e.”

In a study by Carlton et al. (1991), an NOAEL of 10 mg/kg-day for reproductive effects in rats receiving gavage doses (0, 2.5, 5, or 10 mg/kg chlo rine dioxide in deionized water) was identified 8

. 2.2.6 Carcinogenicity The sodium chlorate and hydrogen peroxide component s of Purate ® are not considered carcinogenic. Additionally, IARC, OSHA and ACGIH d o not list hydrogen peroxide as a carcinogen and animal experiments did not show clea r carcinogenic evidence in different species. (See Purate ® MSDS in GESAMP submission).

Sulfuric acid is not considered to be, nor suspecte d to be, a cancer-causing agent. (See sulfuric acid MSDS in GESAMP submission).

Chlorine dioxide has not been assessed for carcinog enic potential. The available dermal carcinogenicity studies do not definitively charact erize the carcinogenicity of chlorine dioxide 3

.
2.2.7 Mutagenicity/Genotoxicity Sodium chlorate is not considered mutagenic. In vitro studies indicate that without metabolic activation, hydrogen peroxide is mutagenic and gene rally not mutagenic with metabolic activation. No mutagenic effects were observed wit h in vivo studies after oral administration. (See Purate ® MSDS in GESAMP submission).

Sulfuric acid is not reported to produce mutagenic effects in humans (sulfuric acid MSDS in GESAMP submission).

From the USEPA Toxicological Review of Chlorine Dio xide and Chlorite 8 :

“Both positive and negative results have been found in genotoxicity studies of chlorine dioxide. Expos ure to chlorine dioxide did not induce chromosomal aber rations in vitro, but it did increase occurrence of reverse mutations (Ishidate et al., 1984). In vivo assays did not find increases in micronucleus induc tion, chromosomal aberrations, or sperm-head abnormalitie s following oral exposure (Meier et al., 1985), but they did find increases in micronuclei induction af ter intraperitoneal injection (Hayashi et al., 1988 ).”

2.2.8 Toxicokinetics
When sodium chlorate was administered on a carrier by capsule in steers, the apparent radiochlorine absorption was approximately 65%. Ur ine was the primary route of elimination where 65-100% of the radiolabeled material was the parent chlorate. Chloride was the only radiochlorine labeled metabolite detected 11

.

11 Smith, D.J., Anderson, R. C., Ellig, E.A., and La rsen, G.L. (2005) Tissue Distribution, Elimination, and Metabolism of Dietary Sodium [36Cl} Chlorate in Beef Cattle.24

From the European Chemicals Bureau Summary Risk Ass essment Report 10 on hydrogen peroxide:

“The toxicokinetic evaluation of H 2 O 2 suggests that only under conditions of very high e xposure rates the substance might enter the systemic circulation. Wh en accidental swallowing is excluded, it is unlikel y that such high exposures could be reached in any realist ic scenario of occupational or consumer exposure. It is especially unlikely that the substance deposited on the skin is systemically absorbed to a meaningful degree. Results from animal studies also suggest t hat local toxicity at the point of contact and no s ystemic effect as the primary mode of action.”

Sulfuric acid is not expected to be absorbed or dis tributed throughout the body 1

.
Seventy two hours after administration of chlorine dioxide in water to rats 12 , 75% of the recovered dose had been in urine and 25% feces. Ch loride ion was the major metabolite accounting for approximately 84% of the administere d dose.

From the USEPA Toxicological Review of Chlorine Dio xide and Chlorite 8 :

“Chlorine dioxide and chlorite are rapidly absorbed from the gastrointestinal tract and slowly cleared from the blood. Chlorine dioxide and chlorite, primarily in the form of chloride, are widely distributed throughout the body and predominantly excreted in t he urine. Chloride is the major urinary “metabolite ” for both chlorine dioxide and chlorite.”

2.3 DATA ON ENVIRONMENTAL FATE AND EFFECT UNDER AER OBIC AND ANAEROBIC CONDITIONS (G9: 4.2.1.3) The active substance and relevant chemical (chlorin e dioxide and chlorite, respectively) are the only constituents potentially present at environmentally relevant concentrations in treated ballast water that may be discharged to the environment. Therefo re, environmental fate is evaluated for these substances only.

2.3.1 Modes of Degradation (Biotic, Abiotic) Degradation of chlorine dioxide occurs by abiotic m echanisms and results from oxidative reactions with target organisms and some organic co nstituents. Degradation also occurs from thermal decomposition, disproportionation, and is e nhanced by ultra-violet (UV) light 2 . Chlorine does not hydrolyze to an appreciable extent but rem ains in solution as a dissolved gas 13

.
Chlorite is more stable in aqueous solution than ch lorine dioxide; however, in a similar manner to chlorine dioxide, chlorite also degrades in aque ous solution as a result of oxidative reactions. In treated ballast water that is discharged, residu al chlorite will decrease through reactions with organic matter to form chloride, which is non-toxic at the concentrations of interest. Chlorite is not persistent as a result of its degradation pathw ay to chloride 2

.
2.3.2 Bioaccumulation, Partition Coefficient, Octan ol/Water Partition Coefficient The water solubility of chlorine dioxide and sodium chlorite is 3.0 g/L and 390 g/L, respectively. These physical properties indicate that bioaccumula tion is not likely. Additionally, the K ow

12 Abdel-Rahman, M.S., Couri, D., and Bull, R.J. (19 82) Metabolism and Pharmacokinetics of Alternate Dr inking Water Disinfectants. Environmental Health Perspective s, v46, pp19-23.
13 EPA Guidance Manual, Alternative Disinfectants and Oxidants, Chlorine Dioxide, 1999.25

values of chlorine dioxide and chlorite are -3.22 a nd -7.17 3 , respectively. Also see Sections 2.1.5 and 5.1.4.

2.3.3 Reaction with Organic Matter Chlorine dioxide is an oxidizing agent. Chlorine d ioxide does not chlorinate organic matter, thus its use does not promote the formation of trihalome thanes (THMs), which are a concern with respect to toxicity and carcinogenicity 2

.
In addition, data collected for the drinking water industry shows that the use of chlorine dioxide results in a reduction of the observed concentratio n of organic contaminant species (e.g., THMs, haloacetic acids (HAAs), haloaldehydes, haloketones , halocarboxylic acids and other potentially harmful organic residues). Similarly, the reaction of chlorite ion with organic matter does not produce harmful organic chemical species and typica lly results in a chemical reduction of chlorite ion to chloride ion, which is ubiquitous i n the marine environment. Therefore, the production of harmful organic by-products is not an ticipated.

2.3.4 Potential Physical Effects on Wildlife and Be nthic Habitats The chemical and physical properties of the prepara tion chemicals, active substance, and relevant chemicals (Table T2-15) indicate that physical effe cts on wildlife and benthic habitats as described and rated in GESAMP Reports and Studies N o. 64 would not be expected to occur. Also see Section 2.1.4.

2.3.5 Potential Residues in Seafood No potential for residues in seafood are known or a nticipated.

2.3.6 Any Known Interactive Effects No other known or expected interactive effects.

2.4 PHYSICAL AND CHEMICAL PROPERTIES FOR THE PREPAR ATIONS, ACTIVE SUBSTANCE, AND TREATED BALLAST W ATER (G9: 4.2.1.4)

Table T2.15 – Physical and Chemical Properties

Physical/Chemical Property (with units & reference) Preparations

1. Purate ®
2. Sulfuric Acid (78% by weight) Active Substance

Chlorine Dioxide (solution) Relevant Chemical

Sodium Chlorite Treated Ballast Water

Melting point (oC) 1. -29 2. -11.3 Same as water (0 oC) Boiling point (oC) 1. 111 2. 193 Same as water (100 oC) Flammability (flash point for liquids; oC) 1. Non flammable a 2. Non flammable Not applicable

Density (20oC; kg/m3) 1. 1370 ca. 2. 1708 1000 - 1035 ca (for dilute sol’n in sea water) Vapor pressure 1. 6700 Pa (40oC, 40% sodium chlorate sol’n) 2. <133.32 Pa (37.8oC) 399.9 Pa (30 oC)

Vapor density (air=1) 1. Similar to water b 2. 3.4 @ boiling 2.326

Physical/Chemical Property (with units & reference) Preparations

1. Purate ®
2. Sulfuric Acid (78% by weight) Active Substance

Chlorine Dioxide (solution) Relevant Chemical

Sodium Chlorite Treated Ballast Water

point

Water solubility (temp; effect of pH; mg/L) 3.0 g/L @ 25oC and 34 mmHg 39 g/100 ml at 17°C

(from solid form)

pH in solution 1. 2 ca 2. <1 (1% aq.sol’n) ca 6.7 - 7.6

Dissociation constant (pKa) 1.72 i 1.72 i

Oxidation-reduction potential 1. Strong Oxidizer 2. Strong Oxidizer 0.95 V @ pH 4-7 ca 100 – 700 mV k Corrosivity to material or equipment 1. See note c 2. Corrosive Produced in situ and delivered to ballast tanks with materials designed for ClO2. Similar to untreated ballast water (see Section 6.1.2) Similar to

untreated ballast water (see Section 6.1.2) Reactivity to container material 1. Yes d
2. Yes e Produced in situ , not stored Autoignition temperature (oC) 1. Not applicable 2. No Data Available Not applicable

Explosive properties Stable as an aqueous sol’n j Oxidizing properties 1. Strong oxidizer f 2. Strong oxidizer g Intended for use as disinfectant/oxidizer Surface tension 1. See note h
2. Not Available Similar to intake water Viscosity (20oC) 1. 1.8 mPa.s 2. 26.7 mPa.s Same as treated sea water The low

concentration will not affect typical sea water viscosity 1060 cP (20oC) (same as sea water)
Thermal stability and identity of breakdown products Avoid elevated temps to avoid/reduce evolution of ClO2 gas. Other physical or chemical properties 1. Liquid slight blue color w/ slightly pungent odor. 2. Dense, viscous, colorless, odorless liquid Pale green/yellow solution with an odor similar to chlorine. -- --

Salinity 23.8 – 24.7 ppt

TOC/DOC, % Particulate Matter 3271 μg/l (TOC) 3073 μg/l (DOC) 6.05% l Shaded cells = data not required

a Contact with organic materials e.g. textiles, woo d or leather may cause fire, if allowed to dry. Co ntamination from various metals or organic materials may cause rapid decompositi on, resulting in oxygen gas release and pressure bu ild-up if not properly vented.
b Purate ®

is a solution of sodium chlorate and hydrogen pero xide containing 52% water. The only relevant vapor present is water vapor.

c Purate ®

is corrosive to carbon steel, copper, and brass. Stainless steel 316 and 316L are suitable. Non-met al materials such as CPVC, PVDF, PTFE, ECTFE, and vinyl ester resins offer excellent performance. Polyethylene and poly propylene offer good performance, typically for storage tanks.

d Materials to Avoid: Incompatible materials and ch emicals such as organic materials, alkaline substan ces, strong acids, phosphorus, sulphur, sulphides, sulphites, and m etal/ammonium salts. Contaminated organic materials ignite readily if allowed to dry. Decomposes in contact with certain metals a nd alkalis, which generates oxygen gas. Risk of exp losion.

e Do not store near bases, halides, sulfides, picrate s, nitrates, chlorates, carbides, fulminates, cyani des, and reducing agents. Do27

not allow water to enter containers. Sulfuric a cid may be safely stored in properly designed bulk storage tanks.

f Contamination from various metals or organic mate rials may cause rapid decomposition, resulting in o xygen gas release. Assists combustion. Contaminated clothing will become hi ghly combustible if allowed to dry, and may be igni ted by friction or heat.

g Sulfuric acid is not flammable or combustible. H owever, it is highly reactive. Concentrated sulfur ic acid is a strong oxidizer capable of igniting combustible materials on con tact.

h No test data is available. Expect it to be similar to a water solution of ionic salts, like sodium ch loride.

i The pKa for chlorous acid (HClO 2 ) is 1.72. HClO 2 ↔ ClO 2 - + H +

j BWTS chlorine dioxide solution (5 mg/L) is >99.5+% water and is generally water-like. Highly concentr ated solutions (>8000 mg/L) can be explosive.

k At higher end of range immediately after chlorine d ioxide treatment, then decreases to values similar to untreated ballast water.

l % Particulate matter calculated as follows: 100* (TOC-DOC)/TOC

2.5 ANALYTICAL METHODS AT ENVIRONMENTALLY RELEVANT CONCENTRATIONS (G9: 4.2.1.5) Chemistries that have been tested and verified by t he USEPA are used to analyze the chlorine dioxide treated ballast water produced by the Ecoch lor ® BWTS. Chlorine dioxide residuals are measured using the lissamine green B (LGB) chemistr y (USEPA Method 327). Chlorite ion residuals are measured by ion chromatography (IC) ( USEPA method 300.1).

Chlorine dioxide measurements are performed using t he Palintest 1000 Chlordiox-Duo Photometer with prepackaged reagent kits to measure chlorine dioxide in the 0.1 to 20 mg/L concentration range. The LGB detection chemistry i s highly selective for chlorine dioxide in the presence of chlorite ion. The prepared reagents es tablish the proper pH to minimize any potential reaction with chlorite ion. The reagent kit also includes a chemical mask to react with chlorine if it is present in the sample. Under th e measurement conditions, studies indicate that the seawater matrix does not create interference is sues that might lead to inaccurate measurements. The recommended operating range is 0 – 40oC, and the test reagents are calibrated for use at 15 - 25oC. For lower or high er sample temperatures equilibration of a particular sample to ambient temperature is recomme nded.

The sensitivity of the Palintest LGB analytical met hod provides field verification of the expected decay of chlorine dioxide in treated ballast water at levels below environmentally relevant concentrations.

Chlorite ion is measured using USEPA Method 300.1. This method uses a sodium carbonate eluent to separate and measure common anions (F - , Cl, NO 2 - , Br - , NO 3 - , HPO 4 2- and SO 4 2- ) as well as chlorite, chlorate and bromate ions. Typically, th e sample (25 to 1,000 μ L) is injected into the eluent at 1.0 mL/min. The sample passes through a metal free column to remove dissolved metals and a guard column before separation on the analyti cal column. An anion suppressor is used with a weak acid regenerant solution (newer IC systems mig ht use electrochemical suppression which is equally effective). Detection is by conductivity.

Method 300.1 may be used to routinely measure chlor ite and chlorate ions from 5.0 μg/L to concentrations in excess of 5.0 mg/L. Measurement at lower concentrations can be made by increasing the sample loop volume. Higher concent rations require a dilution to bring the sample concentration to a level inside the calibration ran ge of concentrations.

The sensitivity of USEPA Method 300.1 provides veri fication of the chlorite ion concentration in chlorine dioxide treated ballast water at levels be low environmentally relevant concentrations.28

2.6 QUALITY CONTROL/QUALITY ASSURANCE (G9: 4.2.4)

2.6.1 Chemical Quality Control

Purate ® is a proprietary chemical formulation manufactured by Eka Chemicals. An outline of the procedure Eka follows to ensure quality of thei r product is included in GESAMP submission.

Sulfuric acid is obtained from different suppliers depending on the location where chemical resupply may occur. Each sulfuric acid supplier prov ides batch control or certificate of analysis documentation. Examples of these documents are inc luded in GESAMP submission.

Chlorine dioxide is generated on demand and quality is assured through preparation chemical quality. Additionally, the operational parameters of the system that are controlled automatically (discussed in Section 3.0) ensure efficiency of chl orine dioxide production. Routine BWTS maintenance also ensures system efficiency and qual ity of the active substance.

2.6.2 Test Data Quality Control Nautilus Environmental has performed toxicity tests for evaluation of the Ecochlor ® BWTS. Quality assurance documentation is included in GESA MP submission.

NovaChem Laboratories, Inc. has performed chemical analysis for Ecochlor. Quality assurance documentation is included in GESAMP submission.

Data quality is also discussed in Section 6.5.2.

3.0 USE OF THE ACTIVE SUBSTANCE

3.0.1 Manner of Application (G9: 4.2.6) As described in Section 1.0, Ecochlor is utilizing a two precursor chemical approach to generate chlorine-free chlorine dioxide onboard. The two pr ecursor chemicals are Purate ® and sulfuric acid. Purate ® , a proprietary chemical from Eka Chemicals, is a m ixture containing 40% by weight (NaCl0 3 ) sodium chlorate and 8% by weight (H 2 O 2 ) hydrogen peroxide. The sulfuric acid is industrial grade 78% by weight (H 2 S0 4 ) acid solution.

The Ecochlor ® BWTS generates and injects a dilute solution of ch lorine-free chlorine dioxide (5.0 mg/L final concentration) into ballast water a s it is loaded onboard. Chlorine dioxide is generated on demand based on the volume of ballast water being brought onboard and is injected immediately. Chlorine dioxide is not stored onboar d as a concentrated substance at any time.

The mechanism of action of chlorine dioxide on orga nisms is not entirely deciphered. However, a study by Aieta and Berg (1986) reported that perm eability of the outer membrane is disrupted by chlorine dioxide 13 . Additional studies supported the findings that o uter membrane proteins and lipids were altered by chlorine dioxide 13

.
During Ecochlor’s early investigations with chlorin e-free chlorine dioxide the target dosage found to be effective on the widest array of organi sms in various water samples was 5.0 mg/L. This target dosage was established by examining the efficacy of chlorine dioxide treated water29

(20°C) at 1.0, 5.0, 10 and 20 mg/L dosages in a lab oratory setting. In developing the target dose, the desired concentration had to be high enough to meet the initial chlorine dioxide demand of a water sample (demand is discussed in Section 2.0.2) , and then a residual concentration of chlorine dioxide had to remain in the water sample long enough to be effective on biofilms and/or AIS in ballast tank sediments. These trials indicated that at a treatment of 1.0 mg/L chlorine dioxide, the chlorine dioxide was quickly consumed and therefore, a residual concentration was not available for disinfection. While chlorine dioxide dosages of 10 and 20 mg/L were effective biocidal treatment, the residua l concentration persisted longer than necessary and was considered an excessive use of ch lorine dioxide.

Therefore, the study demonstrated that chlorine dio xide applied at a dose of 5.0 mg/L is safe, effective, and economical. Treatment at 5.0 mg/L n eutralizes all forms of AIS and then remains effective to neutralize any biofilm or AIS that mig ht be present in the ballast system and ballast tanks.

In the significant number of tests that Ecochlor ha s conducted on treated ballast water, the typical time required for chlorine dioxide to decay to a no n-detectable concentration is less than 24 hours. In waters that are colder or warmer, or hav e lower or higher levels of organic matter, decay rates may decrease or increase. The 5.0 mg/L target dosage and subsequent residual concentration time (i.e. holding time) ensures effe ctive removal of AIS and a zero concentration of chlorine dioxide in treated ballast water at the time of discharge.

3.0.2 Operational Overview & Process Description
The Ecochlor ® BWTS consists of two self-contained chemical stora ge modules, two separate precursor chemical pumps, a chlorine dioxide genera tion module (housing for the reactor column), a booster pump, a programmable logic contr oller (PLC), an operator interface terminal (OIT), a system status/start-up panel, and piping t o inject chlorine dioxide solution into the ballast water line. Ancillary equipment includes p ipelines for chemical vents and re-supply, and in-line sampling valves. For demonstration, an eng ineered drawing of a full scale Ecochlor ® BWTS is included in GESAMP submission. Figure F3.1 provides a photograph of the Ecochlor ® BWTS and F3.2 outlines the Ecochlor ® BWTS process.30

Motive Water Figure F3.1 – Photo of Full Scale Ecochlor ® BWTS

Figure F3.2 – Ecochlor ® BWTS Process Flow Diagram

FT = Flow Transmitter, PT = Pressure Transmitter, P LC = Programmable Logic Controller

With Eka’s SVP-Pure ® chlorine dioxide generator, individual chemical pu mps transfer the Purate ® and sulfuric acid to the reactor column within the chlorine dioxide generation module. The reactor column is under vacuum and is continuou sly monitored using a pressure transmitter to ensure the generation of chlorine dioxide is und er sub-atmospheric conditions. Loss of vacuum for any reason (loss of water flow, power, e tc.) will automatically shut down the system and stop chlorine dioxide production. Inside the r eactor column, the chemicals react to form To Ballast Tanks

Venturi Eductor31

chlorine dioxide, oxygen, sodium sulfate and water. (Refer to Section 2.0 for a detailed discussion of the chemistry.)

At no time during the production or injection of ch lorine dioxide are any chemicals open to the atmosphere. All chemicals are completely contained in appropriate storage vessels or pipelines during the entire treatment process. All aspects o f the treatment process take place under conditions that are highly controlled and monitored automatically at all times. Chlorine dioxide is generated on demand based on the volume of balla st water being brought onboard and is injected immediately. Chlorine dioxide is not stor ed onboard at any time.

3.0.3 System Monitoring & Control, Crew Interaction
The Ecochlor ® BWTS is designed to provide a safe, economical and completely effective solution to the problem of AIS in ballast water. I t is also designed to minimize impacts to existing cargo and ballasting operations, crew acti vities, and demands of the vessel (power, water, etc.). The Ecochlor ® BWTS is fully automated and, depending on how auto mated the ships’ ballast water system is, typically requires no additional actions by the crew or alteration of current ballasting procedures. However, more “manu al” ballast water systems that do not have electronic monitoring capabilities may require slig ht alterations in current ballasting procedures to avoid conditions that the Ecochlor ® BWTS could falsely recognize as unacceptable. Min or modifications to ballasting procedures, if any, are ship specific and carefully considered during system engineering and installation.

If at any time during the ballasting operation the parameters required for safe operation are not met, the BWTS automatically stops production of chl orine dioxide. An alarm is given and the condition resulting in the alarm is displayed on th e OIT. A list of system alarms and the appropriate response for each are provided during E cochlor’s training of ship’s crew and are kept with the system. Should an alarm condition occur, reactivating the system requires that the condition be recognized. Once addressed, the alarm is reset on the OIT. Once reset, the PLC will again perform the series of run permissives an d resume chlorine dioxide production. Further discussion on the BWTS alarms and safety capabiliti es can be found in Section 3.0.7. The reliability of Eka’s chlorine dioxide generators is discussed in Section 3.0.5.

3.0.4 System Requirements Power Requirements: The power requirements for the Ecochlor ® BWTS are quite small. These are: 480 VAC, 3-phase, 60 Hz, rated at 16 FLA. Th e PLC panel requires 1-phase, 60Hz, 220 VAC rated at 2 FLA.

Water Requirements: As discussed above, a small amount of motive wate r flow (approximately 53 L/min) is required for a system treating 2,500 m 3 /hour of ballast water. The water can be fresh or sea water, and is utilized to create a vac uum in the reactor column. This vacuum draws the chlorine dioxide into solution for delivery to the ballast water system.

Space Requirements: The Ecochlor ® BWTS can be completely enclosed within the dimensi ons of a standard shipping container, or a custom desig n can be developed to accommodate a specific vessel’s requirements. One of the two systems curr ently installed is fully enclosed in a container with dimensions of 5.03 m x 1.98 m x 2.34 m. The o ther system was designed to meet the32

requirements of the space and is not fully enclosed , with a small footprint measuring approximately 7.5 m 2

.
Personnel Requirements: The Ecochlor ® BWTS was designed to require minimal input from technicians and/or crew members. In most installat ions, the system is kept in an “enabled” or idle state until the PLC detects a ballasting opera tion. The crew member performs the ballasting procedure as normal (gravity, pump, etc,) and the E cochlor ® BWTS automatically treats incoming ballast water. The BWTS also determines w hen ballasting has stopped and conducts a pre-determined shut-down procedure to flush residua l chlorine dioxide from the reactor column and injection piping. The BWTS returns to an idle state until the next ballasting operation is detected by the PLC.
For installations on ships with a more manual balla sting system that is not capable of electronic signals, a crew member may be required to push a ‘s tart’ button or switch on a control panel after the ballasting operation has been initiated. The B WTS will then operate and control chlorine dioxide production automatically as described above . No further crew member action is required to stop chlorine dioxide production as the PLC will recognize when the ballasting operation has terminated, perform the shut-down procedure and ret urn to the idle status.
Maintenance Requirements: The chlorine dioxide generator requires approxima tely 6 hours of preventative maintenance per year. Ecochlor techni cians will conduct this service during routine technical service visits. The scheduled maintenanc e can easily be accomplished during a typical port call and will be conducted when the BWTS is no t needed for treatment of ballast water.

Maintenance that involves chemical inventory or re- supply will always be handled by Ecochlor technicians, and never ships’ crew.

3.0.5 System Locations, Considerations and Limitations
Locations and Considerations: The most important factor in the safe operation of the Ecochlor ®
BWTS is to first determine a suitable location. So me of the factors that must be considered for placement of the Ecochlor ® BWTS are:

• General space limitations – what engineering will b e required to fit the system in the desired location?

• Is there a location available that does not interfe re with normal cargo operations or required crew activities?

• Can motive water and electricity be provided in a s afe and practical manner?

• Can chlorine dioxide solution piping be routed to t he injection point in a safe and practical manner?

• Can the precursor chemicals be re-supplied easily o r can the chemical storage units be easily removed and re-supplied land based?

• Is the area’s cleanliness acceptable? The area aro und the Ecochlor ® system should be clean and free of debris.

The Ecochlor ® BWTS can be located in any suitable and convenient location dependant on the ship’s design. Ecochlor’s naval architects look fo r placement opportunities close to the main ballast water pumps to minimize the length of pipin g needed for any given installation.33

Limitations: Incoming or Raw water

Chlorine dioxide was selected for treatment of ball ast water because of its ability to work effectively under extremely varied water quality co nditions. Ecochlor is confident that the various water conditions found around the world are well within the operational parameters of the BWTS and chlorine dioxide effectiveness. For e xample, chlorine dioxide is effective in brine water (deep oil well applications), high solids app lications (paper mill thick stock, 5 % by weight) and high color / high organic loading appli cations (paper mill, drinking water pretreatment) 14

.

The Ecochlor ® BWTS requires no pretreatment of the ballast water to be effective. This means that high solids or color need not be filtered or r emoved for the chlorine dioxide to be effective against potential AIS. Also, the Ecochlor ® BWTS can easily handle the temperature variations likely encountered in ballast water at different po rts world wide, which are mild compared to many other applications where chlorine dioxide tech nology is successful.

3.0.6 BWTS Operational Safety Features and Alarms Safety Valve Isolation of the BWTS from the Ship’s Ballast System: The Ecochlor ® BWTS and the ships ballasting system are interconnected only by the delivery line/injection quill for injecting the chlorine dioxide solution into the ba llast water and, in the case where the ballast water is used as motive water, the incoming water l ine from the ballast system to the Ecochlor ® BWTS. These lines are fitted with safety valves th at separate the BWTS from the ship’s systems in case of an emergency. These safety valves, toget her with the failsafe measures in the PLC that shut down the BWTS in the event that all run-permis sive criteria are not met, protects the ship’s integrity and assures safe operating conditions. Th ese safety valves have the appropriate approvals by the ship’s classification society and are constructed of materials appropriate for the application. Additional discussion regarding safet y is included in Section 6.2.

System Parameter Alarms: The single most important driving factor in all o f Ecochlor’s design, manufacturing, and installation decisions of any Ec ochlor ® BWTS is safety. In light of this, the Ecochlor ® BWTS requires multiple and redundant system parame ters to be met prior to the activation of the system and subsequent production of chlorine dioxide. Should any of the parameters not be met, the system will not function and chlorine dioxide will not be generated.

The Ecochlor ® BWTS will provide alarms and indicate which parame ter is not to specification. Technicians and/or the ships’ crew can be alerted t o an alarm condition in a variety of ways depending upon the specific needs of each crew and vessel. For instance, the alarm can be sent to a lighted control panel in the engine room, disp layed on an OIT, or an audible signal can be sent to the crew radio communication system. Corre ctive action may be taken by shipboard personnel if it falls within the guidelines establi shed by Ecochlor, or Ecochlor will service the installation on-site should it be necessary.

3.0.7 Precursor Chemical Storage, Handling and Delivery Ecochlor’s team has accumulated over 100 years of i ndustrial and municipal experience in storing, feeding and re-supplying these and many ot her chemicals. This experience is utilized in the design, fabrication and installation of the Eco chlor ® BWTS. Ecochlor also utilizes a team of

14 Simpson, G.D., Miller, R.F., Laxton, G.D., Clement s, W.R., A Focus on Chlorine Dioxide: The “Ideal” B iocide.34

Naval Architects and Marine Engineers from Seaworth y Systems, Inc. to assist with the specifics of shipboard installation and environments.

3.0.8.1 Chemical Storage The two precursor chemicals (Purate ® and sulfuric acid) are stored onboard in tanks des igned specifically for this service. Exact tank specific ations such as size and location are determined according to conditions specific to each ship. The amount of the preparation chemicals kept on board will depend on the ballast water capacity of the vessel. Ecochlor designs the system and performs calculations so that enough chemicals are kept onboard to ensure effective ballast water treatment and achieve a re-supply schedule of two t o three times per year. For the two Ecochlor systems currently installed, the tanks are designed to hold a maximum of approximately 1.14 m 3 of each preparation chemical. Future systems may h ave higher or lower chemical volumes depending on the nature of the specific ballast wat er requirements and refill capabilities.

The Purate ® is stored in a stainless steel tank designed for t his application. Purate ® can be safely stored in a vented stainless steel tank for extende d periods of time. Tanks for Purate ® storage are constructed of 316L stainless steel that is passiva ted prior to the introduction of Purate ®

.

The sulfuric acid is stored in a steel tank lined w ith Halar (ECTFE) to a minimum thickness of 1.5 mm. This coating is recommended for this appli cation by the coatings manufacturer 15 . It is important to note that sulfuric acid is the world’s most commonly utilized commodity chemical. Sulfuric acid is often referred to as the “king of chemicals”, and is produced in greater amounts than any other chemical besides water 16 . Many applications have utilized this material sa fely for many years, often delivering the acid via ocean fre ight.

The chemical storage tanks are designed with second ary containment that has a capacity of 130% of the tanks volume, assuming a 30 degree vessel li st, and are approved by each ship’s classification society (Lloyd’s & ABS). Each Ecoch lor ® BWTS will be equipped with the appropriate spill containment supplies in the unlik ely event of a chemical release.

Chlorine dioxide is generated on demand, is never t ransported to the ship, and is never stored onboard.

3.0.8.2 Chemical Handling Re-supply of the precursor chemicals will be the on ly time these chemicals are ever “handled” during the use of the Ecochlor ® BWTS. The logistical details involved will vary b ased on a variety of factors for each specific ship such as t he type of vessel, the geographic location where re-supply will occur, and where the fill station is installed on the vessel. Ecochlor is capable of conducting chemical re-supply operations at port fa cilities world wide. ONLY Ecochlor technical representatives or highly qualified contr actors trained by Ecochlor will perform resupply operations. Ships’ crew, longshoremen, stev edores, and any other port facility workers will never be required to handle the precursor chem icals at any time.

15 Mosser, Mark L., Sermatech International Inc., Sep tember 15, 2005
16 The Sulphur Institute Online, Glossary of Terms, (http://www.sulphurinstitute.org/webarticles/anmvie wer.asp?a=109&z=30)35

The Ecochlor system does not give off fumes or gase s during normal operation. However, a small amount of fumes may be displaced when the che mical storage tanks are refilled, and sufficient ventilation is necessary during these op erations. For this reason, the chemical tanks are equipped with vent lines. Each Ecochlor ® BWTS installation considers proper chemical storage tank ventilation, preferably to atmospheric conditions such as the weather deck or overboard. The locations of the chemical tank vent lines are placed to ensure that technicians, ship or port crews are not at risk of inhalation da ngers during chemical re-supply operations.

For an installation where venting the chemical tank s to the atmosphere is not possible, placement of the Ecochlor ® BWTS in a suitable location where proper ventilati on can be achieved is necessary. To be more specific, proper ventilation would ensure that the occupational exposure limits for Purate ® and sulfuric acid in air are not exceeded (MSDS she ets in GESAMP submission) include exposure limits for each chemic al). The flow rate to ensure these limits are not exceeded is dependent upon the engineering spec ifics the installation (size of the space where the tanks are located, volume of chemical vapors di splaced, etc.). Therefore, it is not practical to provide an exact air flow rate that may be required for a particular installation. However, the ventilation rate would ensure the occupational limi ts are not exceeded.

Most important for an installation where venting th e chemical tanks to the atmosphere is not possible, is selection of a suitable location on th e ship where existing ventilation mechanisms are in place. An example is a Ro-Ro deck. The cargo o perations that take place normally on Ro-Ro decks can produce harmful vapors. As such, the exi sting ventilation equipment is in place to comply with the occupational exposure limits of a l arge volume of potentially harmful vapors. The rate of air exchange required for such cargo op erations will exceed the necessary air exchange rate for the small amount of chemical vapo rs that might be displaced during a chemical refill operation.

To summarize, Ecochlor’s preferred method for chemi cal tank ventilation is to the atmosphere, in a location that will not create inhalation dange rs for technicians, ship or port crews. Should ventilation to the atmosphere not be possible, plac ement of the system where existing ventilation methods are already in place will ensure the occupa tional exposure limits are not exceeded. It is also important to note that vapor displacement from the chemical tanks is not continual. Vapors will only be displaced from the chemical tanks duri ng refill operations, which are anticipated to occur at a frequency of two - three times per year.

The unloading of foreign materials into the Ecochlo r ® BWTS chemical storage tanks could cause a dangerous event. The chemical fill lines are pla ced away from other lines for loading/unloading, are clearly labeled, and secured (locked) to minimize the chance for misdelivery of material. Additionally, the chemical f ill line fittings for Purate ® are unique and different from those of the sulfuric acid fill line fittings.

The unloading practices and safeguards are outlined by the manufacturer’s MSDS of the two precursor chemicals. The Purate ® and sulfuric acid MSDS sheets, as well at the Pura te ® Technical Bulletin provided by Eka Chemicals / Akzo Nobel, are included in GESAMP submission.36

Only highly trained Ecochlor technicians or represe ntatives will conduct re-supply of precursor chemicals. This will ensure the proper procedures are followed at all times. No crew assistance is needed in the chemical handling procedures, but proper notification and scheduling is mandatory.

For general safety, awareness training of the ship’ s crew is required and performed by Ecochlor or its trained representatives. Additional health and safety discussion is included in Section 6.2.
3.0.8.3 Chemical Delivery The piping used for delivery of the sulfuric acid t o the chlorine dioxide generation module is HastelloyTM (C22 and C276), while the pipe for deliv ering the Purate ® to the generation module is 316 stainless steel. The pipe used to carry the motive water to the Ecochlor ® BWTS is typically a 2” Bondstrand TM pipe. This is the same type of pipe used to carry the chlorine dioxide solution to the injection point. Bondstran dTM pipe has been approved for this service by both ABS and Lloyds.

3.0.8 Various Procedures and Management Measures
3.0.8.1 Fire As with any fire, human exposure to fire, smoke, fu mes or combustion products will be prevented by utilization of proper personal protect ive equipment (PPE). Also, non-essential personnel will be required to evacuate the fire are a.

Purate ® is non-flammable in solution; however, organic mat erials (e.g. textiles, wood, or leather) saturated with Purate ® may increase the potential for fire if allowed to dry, and a heat or ignition source is applied. A fire involving Purate ® is to be extinguished with water or a water spray. The use of dry foam, powder or carbon dioxide type extinguishers is to be avoided. Purate ® will sustain combustion due to release of oxygen upon th ermal decomposition. Refer to the Purate ® Material Safety Data Sheet (MSDS) that is included in GESAMP submission for complete fire procedures.

Sulfuric acid is not flammable or combustible and i s not sensitive to static discharge or mechanical impact. However, it is highly reactive and concentrated sulfuric acid is a strong oxidizer capable of igniting combustible materials. A fire involving sulfuric acid is to be extinguished with dry chemical, carbon dioxide or f oam extinguishing agents. A fire area may be flooded with water, or fire-exposed containers m ay be kept cool with a water spray, but water shall not be allowed to enter containers of sulfuri c acid. Decomposition of sulfuric acid under fire conditions will produce sulfur oxides. Refer to the sulfuric acid MSDS that is included in GESAMP submission for complete fire procedures.

3.0.8.2 Accidental Release Measures Ecochlor technicians and ship’s crew will be suffic iently trained to respond to a chemical spill situation. Training will include, but may not be li mited to, familiarization of the chemical properties and reactivity, exposure hazards, and co rrect donning of PPE. Proper PPE will include respiratory protection equipment, eye and f ace protection (goggles and/or face shield), chemical resistant gloves and boots (or boot covers ), and chemical resistant clothing.37

Any accidental chemical release requires isolation of the spill area and evacuation of nonessential personnel. Proper PPE is to be worn, goo d industrial hygiene practices will be maintained and adequate ventilation will be used in any area of accidental release.

For both Purate ® and sulfuric acid, suitable dry, inert materials t hat are not combustible (sand, earth) or sorbents that are designed for use with t hese chemicals will be used to absorb spills. Chemical spill containment kits and PPE are kept ne ar the BWTS in the event of a chemical release. Used absorbent materials will be placed i n appropriate chemical waste containers for proper disposal.

3.0.8.3 Marine Environment Release The preparations, although they should not be allow ed to freely enter the marine environment, will not create surface impacts such as oil slicks or thick sludges because both substances are ionizable in water. Should a marine environment re lease occur the proper agencies/authorities will be notified.

If contained, a Purate ® spill can be handled and disposed of as a chemical waste. If released into the marine environment, the Purate ® will readily dissipate as the solution is totally miscible in water. No practical methods of decontamination in a marine water body are available.

Neutralization of sulfuric acid can be achieved wit h sodium bicarbonate, crushed limestone or agricultural lime. This product does not contain a ny components which are designated by the US Department of Transportation to be Marine Pollutant s (49 CFR 172.101).

3.0.8.4 Active Substance Waste Management, Reuse, Recycling , Neutralization Because the active substance is generated on demand and applied in situ, no active substance waste stream is created during the treatment proces s.

3.0.8.5 Conditions for Controlled Discharge Because the active substance is generated on demand and not stored on board, a situation where unwanted chlorine dioxide needs to be discharged is not anticipated.

In the very unlikely event that the precursor (prep aration) chemicals need to be removed from the vessel, the necessary chemical transfer pumps, discharge piping and vessel-specific protocols will be onboard the vessel.

3.0.10 Evaluation of Management Measures Preventing exposures and emergency situations begin s with proper engineering and construction of systems that are designed for use onboard ships. The measures utilized in managing the chemicals associated with the Ecochlor ® BWTS consider system placement, proper training, a nd substance handling that will avoid uncontrolled or emergency situations. The management measures discussed in Section 3.0.9 above are consi dered adequate to properly manage the Ecochlor ® BWTS chemicals in a safe manner.38

4.0 HAZARD CLASSIFICATION & MATERIAL SAFETY DATA SHEETS (G9: 4.2.7) The hazard classifications presented in this sectio n reflect hazards only and do not consider actual potential for exposure.

4.0.1 Purate ® The hazard classification presented below for Purat e ® is according to the European Union directive on classification of hazardous preparatio ns (1999/45/EC). Complete information is included on the Purate ® MSDS provided in GESAMP submission.

R-phrases: R9, R22, R36, R51/53 S-phrases: S3/4, S36/37/39, S46, S61

4.0.2 Sulfuric Acid The hazard classification presented below for sulfu ric acid data from International Chemical Safety Cards (ICSC #0362). Additional information is provided on the sulfuric acid MSDS provided in GESAMP submission. R-phrases: R35 S-phrases: S1/2, S26, S30, S45

4.0.3 Chlorine Dioxide The hazard classification presented below for chlor ine dioxide solution generated with the SVPPure ® technology is according to the European Union dire ctive on classification of hazardous preparations (2001/59/EC). Additional information is included on the chlorine dioxide MSDS provided in GESAMP submission.

R-phrases: R20, R36/37/38 S-phrases: S24/25, S26, S36/37/39

4.0.4 Sodium Chlorite Utilizing a typical MSDS sheet for sodium chlorite solution for hazard classification does not accurately represent the potential hazards at the l ow concentration of chlorite ion that may be present in treated ballast water. Thus, hazard cla ssification is not provided for chlorite ion, but toxicology data is presented in this application.

5.0 RISK CHARACTERIZATION

5.1 SCREENING FOR PERSISTENCE, BIOACCUMULATION, & T OXICITY (G9: 5.1) Biocide treatment of water can raise questions rega rding the formation of THM’s and/or HAA’s. Chemical analysis and known chemical principles of disinfection using chlorine dioxide that is generated in the chlorine-free method used with the Ecochlor ® BWTS indicate that these reaction by-products are not present at environmentally rele vant concentrations. As such, THM’s and HAA’s are not evaluated in regards to persistence, bioaccumulation and toxicity in this application. Chemical data and justifications rega rding these substances are located in Sections 1.0.1 and 2.0.3.3.39

5.1.1 Persistence (G9: 5.1.1.1) Chlorine dioxide and chlorite ion demand/decay data presented in Section 2.0 demonstrate that these constituents do not persist for extended peri ods of time in water. These findings are supported by the physical and chemical properties ( i.e. high solubility, non-organic) associated with these substances as well as studies conducted by others.

For chlorine dioxide, Cooper et al. (2007) demonstr ated that chlorine dioxide degradation is photochemically-enhanced 2 . Fisher and Burton (1993) reported that at 25°C, 60% of chlorine dioxide decays to chlorite within 15 minutes, and d ecayed completely within four hours 2

.
Chlorite is more stable in aqueous solution than ch lorine dioxide; however, in a similar manner to chlorine dioxide, chlorite also degrades in aque ous solution as a result of oxidative reactions. Residual chlorite ion in treated ballast water will decrease through reactions with organic matter to form chloride, which is non-toxic at the concent rations of interest. Chlorite is not persistent as a result of its degradation pathway to chloride 2

.
5.1.2 Bioaccumulation (G9: 5.1.1.2) The estimated log K ow of chlorine dioxide is -3.22 and for sodium chlori te is -7.17 3 . These values along with the chemical properties (i.e. hig h solubility, non-organic) of chlorine dioxide and chlorite indicate that bioaccumulation is not e xpected.

5.1.3 Toxicity (G9: 5.1.2.3)

5.1.4 PBT Criteria - Active Substance (G9: Table 1)

Table T5.1 – PBT Criteria for Chlorine Dioxide & Ch lorite Ion

Substance Persistence (P)

Half-life: >60 days in marine water, or >40 days in freshwater, or >180 days in marine sediment >120 days in freshwater sediment Bioaccumulation (B) BCF >2,000 or Log K ow

≥ 3 Toxicity (T)

Chronic NOEC <0.01mg/L

Chlorine dioxide 3.9 minutes, clear freshwater at 5 meters 2
Criteria fulfilled - No -3.22 3

Criteria fulfilled - No Lowest chronic NOEC = 0.09 mg/L (see Table T2.5) Criteria fulfilled - No

Chlorite Ion <1 hour in saltwater (See Figure F2.4) Criteria Fulfilled – No -7.17 3 (as sodium chlorite) Criteria fulfilled - No Lowest chronic NOEC = 0.18 mg/L (See Table T2.5) Criteria Fulfilled - No

It is important to note that the half-life of chlor ite ion reported is based on laboratory analysis with a raw sea water sample. The decay rate in ano ther water sample may be shorter or longer, depending on the organic matter present and water t emperature. However, this analysis is consistent with the well-documented decay behavior of chlorite ion indicating that persistence >60 days in sea water would not be expected.40

The estimated log K ow values for chlorine dioxide and chlorite, the phys ical and chemical characteristics (i.e. highly soluble, non-organic), along with well-documented degradation behavior, indicate that chlorine dioxide and chlori te ion will not bioaccumulate. Additionally, neither chemical meets the criteria to be classifie d as PBT substances.

5.2 EVALUATION OF THE TREATED BALLAST WATER

5.2.1 Determination of Holding Time 5.2.1.1 Toxicity and Dilution of Treated Ballast Wa ter Nautilus Environmental performed toxicity testing o n treated ballast water 2 (See Tables T2.9 and T2.10). Mytilus sp. bivalve larval development and Mysidopsis bahia acute toxicity tests were selected because these species were identified as b eing the most sensitive to chlorine dioxide and chlorite, respectively. An acute toxicity test was selected for M. bahia due to the small difference in the acute test EC50 (0.58 mg/L) and t he chronic test NOEC for chlorite (0.18 mg/L). Thus, the acute-to-chronic ratio (acute LC5 0 divided by chronic NOEC) for M. bahia for chlorite was 3.22 2

.
Results of toxicity tests with treated ballast wate r using Mytilus sp. (chronic) and Mysidopsis bahia (acute) are presented on the basis of percent by v olume (% v/v) of treated water.

No chronic toxicity was observed with the Mytilus edulis larval development test for treated ballast water; the EC50 was greater than the highes t test concentration in each of two tests (>81% and >84% v/v).

Acute toxicity with M. bahia resulted in EC50 values of 38.7% and 37.7% (v/v) a nd the NOEC for both tests was 25% sample. Thus, a three-fold dilution was necessary to reach a concentration less than the EC50 and a four-fold di lution was necessary to result in no acute toxicity with M. bahia . Because M. bahia was the most sensitive species to chlorite by a significant margin, these data can be considered ap propriate to evaluate safe concentrations for aquatic organisms.

Although chronic toxicity tests were not conducted with treated ballast water using M. bahia

, evaluation of the dilution necessary to result in a chronic toxicity NOEC was calculated. Based on acute EC50 values (38.7% and 37.7%) and an acute -to-chronic ratio of 3.22, the NOEC for chronic effects is calculated to be 12% and 11.7% ( EC50 value divided by 3.22 ratio). Thus, a dilution to approximately 12% (v/v) would achieve n o chronic toxicity to M. bahia , which has been demonstrated to be the most sensitive species by a significant margin in the tests performed 2 . Further, the next most sensitive species ( A. affinis , chronic NOEC 13.8 mg/L) was almost two orders of magnitude less sensitive to ch lorite. Consequently, application of a 10-fold safety margin is likely highly conservative 2 and protective of aquatic organisms.

5.2.1.2 Factors Influencing Holding Time As presented in Section 3.0.1, the 5.0 mg/L target dosage and subsequent residual concentration time (i.e. holding time) ensures effective removal of AIS and an undetectable concentration of chlorine dioxide in treated ballast water at the ti me of discharge. This target dose of chlorine dioxide treatment was developed to use the smallest concentration possible for safe and economical treatment of ballast water.41

Shipboard testing of chlorine dioxide demand has in cluded seasonal changes in North America (North East, Pacific North West, Gulf Coast), Centr al America (Pacific), Sweden, and North Africa. The conclusion is that temperature is the most critical factor in determining the length of time for the chlorine dioxide residual to decay to undetectable concentrations in ballast water tanks. However, through extensive shipboard testin g and laboratory analysis, chlorine dioxide decay is predictable.

In the significant number of tests that Ecochlor ha s conducted on treated ballast water, the typical time required for chlorine dioxide to decay to a no n-detectable concentration is less than 24 hours. In waters that are colder or warmer, or hav e lower or higher levels of organic matter, decay rates may decrease or increase. Decay rates (i.e. demand) of chlorine dioxide in various waters at differing temperatures are presented in S ection 2.0.2. Ecochlor has found that lower temperatures can lengthen the time required to reac h an undetectable level of chlorine dioxide, while higher temperatures typically increase the de cay rate. Ecochlor takes this into account in developing and applying the treatment methodology.

One significant advantage of chlorine dioxide treat ment is its ability to remain effective in a broad range of pH values. The lack of any signific ant reaction of chlorine dioxide with water is partly responsible for retention of biocidal effect iveness over a wide pH range 14 . The typical pH ranges found in various natural waters will not aff ect the anticipated decay rates or the holding time for effective chlorine dioxide treatment.

Based on laboratory and shipboard tests, salinity d oes not interfere with chlorine dioxide’s oxidative properties or alter the effectiveness of chlorine dioxide treatment. Ecochlor has found that the decay rate of chlorine dioxide in fresh wa ter can be slower that that of salt water. However, the chlorine dioxide demand of a particula r water sample is more related to the amount of organic matter and/or AIS present in the water r ather than salinity.

Another advantage to chlorine dioxide treatment is its ability to disinfect without a need for filtration. Sediment loading does not alter the ef fectiveness of chlorine dioxide treatment of ballast water. However, sediment loading may have an effect on the chlorine dioxide demand of a particular water sample.

Although the chlorine dioxide demand of various wat ers may change, the overall effectiveness and holding time required for chlorine dioxide trea tment of ballast water remain stable. Ecochlor is confident in the holding time (less than 24 hour s) that has been developed for effective treatment of AIS in ballast water.

5.3 RISK CHARACTERIZATION & ANALYSIS

5.3.1 Reaction with Organic Matter (G9: 4.2.1.3) Chlorine dioxide is an oxidizing agent. Chlorine d ioxide does not chlorinate organic matter, thus its use does not promote the formation of trihalome thanes (THMs), which are a concern with respect to toxicity and carcinogenicity 2

.42

In addition, data collected for the drinking water industry shows that the use of chlorine dioxide results in a reduction of the observed concentratio n of organic contaminant species (e.g., THMs, haloacetic acids (HAAs), haloaldehydes, haloketones , halocarboxylic acids and other potentially harmful organic residues).

Similarly, the reaction of chlorite ion with organi c matter does not produce harmful organic chemical species and typically results in a chemica l reduction of chlorite ion to chloride ion, which is ubiquitous in the marine environment. The refore, the production of harmful organic byproducts is not anticipated.

5.3.2 Characterization of Degradation Route & Rate (G9: 5.3.5) Chlorine dioxide degrades rapidly in marine and fre sh waters, predominantly forming chlorite ion as a degradation by-product 2 . Degradation is by abiotic mechanisms and is typi cally a result of oxidative reactions with target organisms and so me organic constituents. Section 2.0.2.1 has figures that demonstrate the decay rate of chlorine dioxide at different temperatures. Based on these laboratory studies, in a static water sample at 24°C treated with 5.05 mg/L of chlorine dioxide had an undetectable concentration within ap proximately 150 minutes (2.5 hours).

Chlorite ion also degrades in aqueous solution as a result of oxidative reactions. The rate at which chlorite ion degrades depends on the demand o f the water. Figures in Section 2.0.3.2 depict laboratory studies on the decay rate of chlo rite ion. In a static water sample at 20°C dosed with 1.94 mg/L of chlorite solution, the concentrat ion of chlorite decayed to 0.19 mg/L in 69 hours. It is important to note that in a laborator y setting where the water sample is in a closed system the chlorite ion concentration becomes stabl e once demand of the water has been met.

5.3.3 Prediction of Discharge & Environmental Conce ntrations (G9: 5.3.8)
When the Ecochlor ® BWTS is utilized as directed by Ecochlor, the conc entration of chlorine dioxide is expected to be at undetectable levels wh en treated ballast water is discharged. Thus, the predicted environmental concentration (PEC) for chlorine dioxide is 0 mg/L.

Figures F2.1 through F2.3 clearly depict the labora tory-derived concentrations of the active substance and relevant chemicals over time with app roximately 5.0 mg/L treatment of chlorine dioxide at three different temperatures. Repeated testing of this type indicates that the curves are predictable. Additionally, ion chromatographic ana lyses of ballast water treated with 5.0 mg/L of chlorine dioxide have measured chlorite ion conc entrations ranging from <0.1 g/L to 2.37 mg/L (see Tables T2.2, T2.3, T2.4, T2.5, T2.6 and T 2.7). Therefore, the PEC for chlorite ion is <0.1 mg/L to 2.37 mg/L. This range is a result of the varied chlorite ion demand of different waters and factors such as organic load, pH and tem perature that affect the decay rate. Section 2.0.3.2 discusses chlorite ion demand /decay in gre ater detail.

The data in Table T2.8 shows no formation of THM’s (<1 μg/L) after treatment of ballast water with chlorine-free chlorine dioxide from the Ecochl or ® BWTS. The table also shows <1 μg/L of HAA’s with the exception of a single haloacetic aci d (dibromoacetic acid (DBAA), which was present at a low level (12 μg/L). These data are consistent with the chemistry of chlorine-free chlorine dioxide as an oxidant. The drinking water standard in the United States is <80 μg/L total THM’s and <60 μg/L total HAA. Therefore, the analysis of treated ballast water43

demonstrates that THM’s and HAA’s are present at le vels well below US drinking water standards, with a PEC’s of <1 μg/L and <1 μg/L to 1 2 μg/L, respectively. Based on chemical analysis and the G9 definition of relevant chemical s under 2.1.4 of the Guideline, Ecochlor does not consider THM’s or HAA’s as relevant chemicals a pplicable to an evaluation of the Ecochlor ® BWTS.

5.3.4 Assessment of Potential for Bioaccumulation ( G9: 5.3.7)
Because the substances utilized with the Ecochlor ® BWTS do not have characteristics that would indicate a potential for bioaccumulation, no bioacc umulation effects are anticipated.

5.3.5 Effects Assessment Acute and chronic toxicity test data for chlorine d ioxide and chlorite are presented in Tables T2.9 and T2.10, respectively.

5.3.5.1 Chlorine Dioxide From the Review of the Environmental Fate and Effec ts of Chlorine Dioxide and Chlorite 2 :

“It should be noted that because of the rapid dissi pation rate of chlorine dioxide, it is somewhat dif ficult to interpret the results of toxicity tests with this c hemical since, unless the system is continually dos ed in a flow-through manner, the test organisms will typica lly be exposed to a concentration of chlorine dioxi de which is diminishing over time, and a concentration of chlorite which is initially increasing (as a br eakdown product of chlorine dioxide) and then itself d ecreasing. Thus, any exposure to chlorine dioxide is actually an exposure to both chlorine dioxide and i ts breakdown product, chlorite, and the extent to w hich each of these toxicants is the cause for any observ ed effect is somewhat difficult to determine. Howe ver, such would be the case in an environment in which a non-continuous discharge containing chlorine dioxi de occurs and, consequently, data from static and stat ic renewal tests with chlorine dioxide appear to be appropriate for this evaluation.”

With respect to risk, toxicity to aquatic organisms appears to be the most significant potential exposure for chlorine dioxide because it is not per sistent in the environment and is not expected to bioaccumulate or adsorb to sediments 2 . An effects assessment of secondary poisoning is not relevant. Therefore, the acute and chronic aquatic toxicity results presented in Section 2.1 for chlorine dioxide provide the most appropriate evalu ation of the potential for adverse effects to aquatic organisms.

Acute toxicity data (LC50 or EC50) are presented in Table T2.9 for survival of the crustacean Mysidposis bahia and the larval fish Menidia beryllina (inland silverside), as well as spore germination of the giant kelp ( Macrocystis pyrifera ). EC50 values for these species were ~0.4, >0.4 and 0.2 mg/L, respectively. Additional data a re presented for survival of a second fish, the Pacific herring ( Clupea pallasi ).

Chronic toxicity data in Table T2.10 include data f or a fish (survival and growth of larval Menidia beryllina ), an invertebrate (survival and growth of a mysid, Mysidopsis bahia ) and an algae (germination and growth of giant [ Macrocystis pyrifera ] kelp spores), as well as for two additional species (larval development for a mollus c [ Mytilus sp .] and population growth for a diatom [ Skeletonema costatum ]). The most sensitive test species was Mytilus sp. , which exhibited a chronic NOEC of 0.09 mg/L and an EC50 o f 0.22 mg/L on the basis of a larval development test.44

5.3.5.2 Chlorite Ion With respect to risk, toxicity to aquatic organisms appears to be the most significant potential exposure for chlorite because it is not persistent in the environment and is not expected to bioaccumulate or adsorb to sediments 2 . An effects assessment of secondary poisoning is not relevant. Therefore, the acute and chronic aquatic toxicity results presented in Section 2.1 for chlorite provide the most appropriate evaluation of the potential for adverse effects to aquatic organisms.

Acute toxicity data (LC50 or EC50) are presented in Table T2.9 for survival of the crustacean Mysidopsis bahia and the larval fish Cyprinidon variegatus (sheepshead minnow), as well as spore germination of the giant kelp ( Macrocystis pyrifera ). EC50 values for these species were 0.58, 75.0 and >15.4 mg/L, respectively.

Table T2.10 includes chronic toxicity data for a fi sh (survival and growth of larval topsmelt, Atherinops affinis ), an invertebrate (survival and growth of a mysid, Mysidopsis bahia ) and an algae (germination and growth of giant kelp [ Macrocystis pyrifera ] spores), as well as for two additional species (larval development for a mollus c, Crassostria virginica and an echinoderm, Strongylocentrotus purpuratus ). The most sensitive test species was Mysidopsis bahia , which exhibited a chronic NOEC of 0.18 mg/L and an EC50 o f 0.25 mg/L on the basis of a 7-day survival and growth test.

5.3.6 Effects on Aquatic Organisms
When the Ecochlor ® BWTS is utilized as directed by Ecochlor, the conc entration of chlorine dioxide is expected to be at undetectable levels wh en treated ballast water is discharged. However, a Probable No Effect Concentration (PNEC) for chlorine dioxide is presented. As defined by the International Maritime Organization (IMO), the PNEC is established at ten times lower than the lowest NOEC in cases where sufficien t data are available. The data provided meet the requirements outlined by the IMO for use o f a 10-fold assessment factor and, consequently, the PNEC for chlorine dioxide is esta blished at 0.009 mg/L 2 (lowest chronic NOEC for Mytilus sp. , 0.09 mg/L divided by 10).

The long-term PNEC for chlorite, as defined by the IMO, is established at ten times lower than the lowest NOEC, in cases where sufficient data are available. The data provided meet the requirements outlined by the IMO for use of a 10-fo ld assessment factor and, consequently, the PNEC for chlorite is established on this basis at 0 .018 mg/L (lowest chronic NOEC for M. bahia, 0.18 mg/L divided by 10). It should be noted that this PNEC is conservative, since a PNEC for chlorite has been reported on the basis of a specie s sensitivity distribution to be 0.135 mg/L by Fisher et al. (2003) on the basis of freshwater acu te toxicity data 2

.

5.3.7 Effects on Sediment
Because the substances utilized with the Ecochlor ® BWTS do not have characteristics that would indicate adsorption to sediment particles, no effec ts on sediments are anticipated.

5.3.8 Comparison of Effect Assessment with Discharg e Toxicity The relevant chemicals (chlorine dioxide and chlori te ion) potentially present in treated ballast water were evaluated in regards to discharge toxici ty. No chronic toxicity was observed with the45

Mytilus edulis larval development test for treated ballast water (see Section 5.2.1.1). Therefore, discharge toxicity testing indicates that observed toxicity in treated ballast water can be attributed to the presence of chlorite.

Samples of ballast water from two separate onboard treatments with 5.0 mg/L of chlorine dioxide were tested for toxicity. Chlorite ion was measured in these samples and was 2.35 mg/L and 0.41 mg/L, which represents both the high and l ow ends of the overall range of chlorite ion measured in treated ballast water. On the basis of measured chlorite ion and the EC50 values of 38.7% and 37.7% by volume, the LC50 for the treated ballast water samples was 0.91 mg/L (2.35 mg/L chlorite multiplied by 38.7%) and 0.15 m g/L (0.41 mg/L chlorite multiplied by 37.7%), respectively. Although these LC50 values a re somewhat variable, their average (0.53 mg/L) compares well with the reported LC50 for chlo rite using Mysidopsis bahia of 0.58 mg/L (Table T2.9). The variability between these two n umbers may have resulted from differences in sensitivity of different batches of test organisms, or variability in subsampling or analytical procedures 2

.
Thus, the results are generally consistent with the conclusion that the toxicity to M. bahia observed in treated ballast water was caused by res idual chlorite and not by chlorine dioxide or additional contaminants. This conclusion is furthe r supported by the fact that toxicity was observed using an acute test with M. bahia in both samples, and no toxicity was observed with a chronic test using Mytilus sp. . In general, a chronic toxicity test with Mytilus sp. would be expected to be more sensitive than an acute test wi th M. bahia in the vast majority of cases, with chlorite being unusual in this regard 2

.

6.0 RISK ASSESSMENT The risks presented by having the Ecochlor ® BWTS onboard are discussed in Section 6.1, while risks to technicians and/or ships crew are discusse d in Section 6.2.

6.1 RISK TO SAFETY OF SHIP

6.1.1 Ship Integrity and the BWTS
The Ecochlor ® BWTS and the ship’s ballasting system are intercon nected only by the delivery line/injection quill for delivering the chlorine di oxide solution into the ballast water and, in the case where ballast water is used as motive water, t he incoming water line from the ballast system to the Ecochlor ® BWTS. These lines are fitted with safety valves t hat separate the BWTS from the ship’s systems in case of an emergency. These safety valves, together with the failsafe measures in the PLC that shut down the BWTS in the event that all run-permissive criteria are not met, protects the ship’s integrity and assures safe operating conditions. The safety valves have the appropriate approvals by the ship’s classi fication society and are constructed of materials appropriate for the application.

Further, the Ecochlor ® BWTS does not become an integral part of the exist ing ballast system upon installation. The ship’s ballast system will run unaffected if the BWTS is enabled/disabled, has power/no power, etc. and the only impact from s hutting off the BWTS would be that incoming ballast water would not be treated.46

6.1.2 Corrosion Corrosion in natural waters, to include seawater an d brackish harbor waters, is caused by the presence of dissolved oxygen, marine growth, and sa lts in the water. Most of the fundamental research on corrosion in natural waters was done in the early part of the 20 th Century and is summarized in the 1948 Corrosion Handbook, edited b y Professor H. H. Uhlig of MIT 17

. Extreme water pH values (below 4 or above 10) can a lso affect corrosion rates.

Figure F6.1 shows the relationship between the salt content of water and corrosion rate. As the salt content increases to approximately 3% by weigh t, the rate of corrosion begins to decrease. This behavior was explained years ago, and is based on the principles of electrical conductivity. As the salt content increases, so does the electric al conductivity. Although increased conductivity increases corrosion rates, the increas ed conductivity is countered by a decrease in the solubility of other substances (such as oxygen) in the water. Because dissolved oxygen is the most common chemical to be reduced by the oxidation of iron 17 , increased salinity reduces the dissolved oxygen in the water, and therefore, reduc es the corrosion rate.

Figure F6.1 – Salt Content and Water Corrosivity 17

1 Effect of Salt Content on Corrosivity of

Water

Note: Redrawn from Uhlig Corrosion Handbook, page 1 31

Since the installation of the first full-scale Ecoc hlor ® BWTS aboard the M/V Atlantic Compass in 2004, testing relating to corrosion has been con ducted. Specifically, the pH and dissolved oxygen (DO) in dockside water as well as chlorine d ioxide treated and untreated ballast water has been measured, and corrosion test coupons have been analyzed by an independent laboratory. The data presented in this section wil l demonstrate that the active substance (chlorine dioxide) being utilized by the Ecochlor ® BWTS does not increase the rate of corrosion above that encountered under typical environmental conditions.

Additionally, installation of the Ecochlor ® BWTS results in no dissimilar metals being in cont act with the existing ballast system or any other part of the ship. All parts in contact with the ship are mild steel. If necessary, Ecochlor can match a particular ship’s alloy piping or identify

17 Heidersbach, Bob; Dr. Rust, Inc.; Ballast Water Co rrosion Rates Using the Ecochlor Ballast Water Trea tment System, May 2007Relative Corrosion Rate

Concentration of NaCl, % wt.47

another appropriate material to ensure there is no elevated risk of corrosion due to use of dissimilar metals.

6.1.2.1 Effect of pH and Elevated Dissolved Oxygen Concentration on Corrosion During a July 2005 investigation aboard the Atlanti c Compass, DO and pH measurements were recorded. The background DO level was measured fro m a sample of Newark, NJ dockside water (FAPS Terminal) and found to be approximately 4.71 mg/L. After the ship completed a ballasting operation, the DO was measured in a cont rol tank (not treated with chlorine dioxide) after the tank was filled (time, T=0). The measure d DO concentration was 5.86 mg/L; a 1.15 mg/L increase in DO compared to the dockside water. At the end of the test period of 96 hours, the DO concentration had dropped to 5.17 mg/L, poss ibly due to the presence of viable respiring organisms.

In the same study, the DO level in a ballast tank t hat received 5.0 mg/L chlorine dioxide treatment was also measured after being filled (tim e, T=0). The measured DO concentration was 6.57 mg/L; a 1.86 mg/L increase in DO compared to t he dockside water. Compared to the control tank, this represents an increase in measur ed DO of approximately 12%. Over the test period of 96 hours, the DO concentration remained r elatively stable and dropped to 6.47 mg/L, possibly due to the lack of respiring organisms. T he results of this study are depicted in Figure F6.2.

Figure F6.2 – Dissolved Oxygen and pH

Dissolved O 2 and pH

0 1 2 3 4 5 6 7 8

0 20 40 60 80 100 Time (h)O2(mg L-1) and pH

O2- C pH- C

O2- T
pH- T

O2- F
pH- F Incoming water FAPS terninal Incoming water FAPS terninal

Source: University of Rhode Island, Graduat e School of Oceanography, 2005 O2 = Dissolved oxygen, C= control (untreate d ballast water), T= treatment (treated ballast wat er) F= Water sample location ID (FAPS Terminal)

Clearly, turbulence that occurs during loading of b allast water, either through a centrifugal pump or gravity, and the turbulent entry into an empty a nd vented ballast tank contributes to an increased DO level in the incoming ballast water. For a chlorine dioxide treated tank, some of the increase observed may also be due to the libera tion of oxygen during the chlorine dioxide48

generation reaction (refer to the chemical equation in Section 2.0.3.1). Based on stoichiometry, when the hydrogen peroxide component of Purate ® reacts with sulfuric acid (at a chlorine dioxide treatment dose of 5.0 mg/L) roughly 1.2 mg/ L of oxygen is generated. This theoretical increase in DO is comparable with that observed dur ing the study. Further, increased DO at these concentrations is not significantly greater t han the increase observed during normal ballasting operations, and is not anticipated to cr eate increased or unacceptable corrosion risk for the ship.

The pH of dockside water (FAPS Terminal) as well as untreated and chlorine dioxide treated ballast water was concurrently measured during the DO investigation. During this study, the pH of the chlorine dioxide treated tank ranged from 6. 61 to 6.82. As Figure F6.2 above demonstrates, the pH of the treated ballast water w as not significantly decreased as a result of chlorine dioxide treatment, and remained stable ove r the duration of the test period. Further, corrosion rates of iron and steel are fairly unifor m between pH’s of approximately 4 and 10. Any change of pH of the ballast tank water between the pH’s of 5 and 9 will not affect corrosion

rates 17

.
6.1.2.2 Corrosion Coupon Testing Corrosion tests have been conducted in ballast tank s treated by the Ecochlor ® BWTS to verify the effect of chlorine dioxide treatment on ballast tank corrosion rates. Tests were conducted with C1010 mild steel corrosion test coupons and se nt to Metal Samples Company, Inc. for analysis 18

.
In July/August of 2005, corrosion test coupons were placed in one control (untreated) tank and one chlorine dioxide-treated tank that received bal last water from Newark, NJ. The treatment tank received a 5.0 mg/L dose of chlorine dioxide. Two test coupons were placed in each tank; one high (approximately 1.35 m from the bottom of a 1.8 m tank) and one low (approximately 0.9 m from the bottom of a 1.8 m tank), and hung by nylon strings. Both sets of coupons remained in the respective tanks for 672 hours (28 days).

In October/November of 2006 a similar test took pla ce in a tank treated with approximately 4.0 mg/L of chlorine dioxide. Two test coupons were pl aced in the tank; one high (approximately 1.35 m from the bottom of a 1.8 m tank) and one low (approximately 0.9 m from the bottom of a 1.8 m tank), and hung by nylon strings. Both coupo ns remained in the tank for 768 hours (32 days).

The results of this initial testing are presented i n Table T6.1 below, and indicate no adverse effect on corrosion rates from chlorine dioxide tre atment. Actually, when the July/Aug 2005 study corrosion rates of test coupons from untreate d and treated tanks are compared, a slight decrease in the corrosion rate was observed for tes t coupons in the treated tanks.

18 Corrosion Analysis Data Report, Metal Samples, Co. , 2005.49 Table T6.1 – Comparison of Corrosion Rates Sample Date ClO2 Dosage (mg/l) Exposure time (Hrs) Corr osion Rate (mpy)

Untreated tank (high) Jul/Aug 2005 0 672 9.8389 Untreated tank (low) Jul/Aug 2005 0 672 10.9133 Treated (high) Jul/Aug 2005 5 672 6.0879 Treated (low) Jul/Aug 2005 5 672 7.87 Treated (high) Oct/Nov 2006 4 768 5.0977 Corrosion by chlorine dioxide

Ecochlor’s statement that chlorine dioxide treatmen t will not adversely affect corrosion rates is supported by this data. Additional verification of these results with continued coupon corrosion studies is planned. Additionally, visual inspectio ns of piping close to the chlorine dioxide injection point will be conducted as necessary duri ng shipyard visits to ensure that there is no sign of excessive wastage.

6.1.3 Fire and Explosion The fire and explosion risks associated with the Ec ochlor ® BWTS relate to the precursor chemicals stored onboard or electrical components t hat are part of the system.

6.1.3.1 Preparation Chemicals As a solution, Purate ® is non-flammable and does not have explosive prope rties 19 . Organic materials (i.e. wood, leather) that become contamin ated with Purate ® can ignite by a heat or friction source if they are allowed to dry. If eva poration of Purate ® solution is allowed, solid sodium chlorate crystals could form. Solid sodium chlorate does not burn, but if exposed to fire it decomposes to give off oxygen, which can feed a fire. Decomposition of Purate ® (in contact with certain metals or alkalis, or upon thermal dec omposition) generates oxygen gas, and has the potential to increase explosion risk.

Sulfuric acid is non-flammable. Although sulfuric acid is not flammable or combustible and is not sensitive to static discharge, it is a strong o xidizing agent and is highly reactive. Concentrated sulfuric acid is capable of igniting c ombustible materials, and contact with water or strong bases can result in a strong exothermic reac tion. Contact with common metals can evolve flammable and potentially explosive hydrogen gas. Sulfur oxides may be produced under fire conditions.

These risks are mitigated through proper training, system engineering, identification of a suitable location for the BWTS, the use of chemical storage tanks specifically designed for the chemicals they hold, and proper tank ventilation. Additional ly, the space where the BWTS is located is kept clean and free of incompatible materials that can react with the precursor chemicals. Regular inspection and maintenance of the BWTS furt her reduce any potential risks. The mitigation measures and engineering controls in pla ce for the precursor chemicals stored onboard make the risks of fire and/or explosion extremely l ow.

19 Physical and Chemical Characteristics of Purate ® , Case Consulting Laboratories, 2000.50

6.1.3.2 Active Substance Gaseous chlorine dioxide can present explosion haza rds under specific conditions. Concentrated vapors of chlorine dioxide gas can be explosive at temperatures >40oC and concentrations >10% v/v in air at 1 atmosphere 20 . However, under the highly controlled conditions that chlorine dioxide is generated with the Ecochlor ® BWTS, the potential for explosion risk is very unl ikely. Section 3.0.7 discusses the safety features of the BWTS that eliminate the possibility of chlorine dioxide production under unacceptable conditions.

Once generated, the chlorine dioxide is immediately converted into a dilute aqueous solution under proper temperature and vacuum conditions in a n enclosed system. In solution, chlorine dioxide is stable and does not present fire or expl osion hazards. Additionally, chlorine dioxide is generated on demand, injected immediately, and neve r stored onboard. Therefore, the risk of fire and/or explosion presented by the active substance is extremely low.

6.1.3.3 Other BWTS Components The electrical components of the Ecochlor ® BWTS are intrinsically safe and there is no risk o f fire associated with this aspect of the BWTS.

6.1.4 Chemical Storage The precursor chemicals (preparations) are the only BWTS chemicals stored onboard at any time. While 78% sulfuric acid is IMDG Code classif ied, the BWTS is considered ship’s equipment and the chemicals are consumables rather than dangerous cargo. Therefore the provisions of the IMDG Code are not applicable (IMD G CODE 2006 Edition, Amendment 33- 06, Chapter VII, Part A. Regulation 2).

The active substance, chlorine dioxide, is generate d on-demand and is never stored onboard.

Outside of the potential fire and explosion risks d iscussed in Section 6.1.3, other risks associated with storing chemicals onboard relate to improper s torage containers. This can lead to unintended chemical release and chemical contact wi th incompatible materials, as well as exposure by direct chemical contact (skin/eye) and/ or inhalation.

Because proper storage containers designed and engi neered specifically for Purate ® and sulfuric acid are utilized with the Ecochlor ® BWTS the potential for unintended release, contact with incompatible materials, or direct chemical exposure to occur is low. (Details of the chemical storage containers are located in Section 3.0.8). To further ensure proper chemical storage, temperature control device(s) can be installed if a BWTS is to be located in an area or on a ship where there is potential for temperature extremes. Additionally, proper training and implementation of standard operating procedures mit igate the potential risks of chemical storage onboard. Should a spill occur, chemical spill cont ainment kits are kept onboard with the BWTS, as well as appropriate fire extinguishing methods. Additional discussion on accidental chemical release is presented below in Section 6.1.5 and the exposure risks to technicians, ship’s crew, and/or other personnel are addressed in Section 6.2 .1 below.

20 Chlorine Dioxide and Chlorite Toxicological Profi le, Agency for Toxic Substances and Disease Registr y (http://www.atsdr.cdc.gov/toxprofiles/tp160-c4. pdf).51

6.1.5 Accidental Chemical Release The potential for unintended release of chemicals a ssociated with the BWTS relate to storage tank failure, delivery pipe failure, and chemical r e-supply operations. The areas for potential release are limited to the areas where the storage tanks are located, where pipelines traverse, and where chemical re-supply operations take place.

6.1.5.1 Storage Tank Failure The risks to a ship of an unintentional release of Purate ® or sulfuric acid from the chemical storage tanks are related to contact with incompati ble materials that may create other hazards such as fire. A chemical release from the storage tanks is very unlikely, and only a catastrophic event on the vessel could result in tank failure an d simultaneous secondary containment failure. As discussed above in Sections 3.0.8, 6.1.3 and 6.1 .4, properly engineered and designed chemical storage tanks and secondary containment, a long with proper placement and maintenance of the BWTS, make the risks to a ship f rom a storage tank failure extremely low.

6.1.5.2 Delivery Pipeline Failure As with any installation where liquids are transpor ted in a pipeline, potential exists for pipeline failure. Should a pipeline failure occur, the risk s to a ship from chemical release include contact with incompatible materials. Although unlikely, th is could increase risk of fire.

Because the BWTS does not compromise the integrity of the ship’s ballast water system (Section 6.1.1), there would be no risk to vessel stabiliy s hould a BWTS piping failure occur. In the event that a pipe failure occurred, emergency stop contro ls to shut down the BWTS are strategically located on the vessel. Additionally, a pipeline fa ilure would create unacceptable conditions within the BWTS, which would be recognized by the P LC and production of chlorine dioxide would cease.

One important factor in mitigating the potential fo r a pipeline failure is selection of proper BWTS construction materials. As presented in Secti on 3.0.8.3, the piping materials were specifically selected for application with the Ecoc hlor ® BWTS to ensure that compatible and sturdy materials are utilized to deliver Purate ® , sulfuric acid and chlorine dioxide.

The risks for pipeline damage are further minimized by installing piping in less exposed areas, using proper labeling, and implementing other prote ctive measures where prudent or required. For installations where the BWTS may be located in a cargo area, extra precautions are taken to eliminate risk of damage to piping. These may incl ude, but are not confined to, installation of hard casings and/or protective barriers around the system where the potential for damage exists.

Preventing exposures and emergency situations begin s with proper engineering and construction of systems that are designed for use onboard ships. Implementation of appropriate mitigation measures ensure that unacceptable risks to a ship f rom chemical release do not result from a BWTS pipeline failure.52

6.2 RISK TO TECHNICIANS AND/OR SHIP’S CREW

6.2.1 System Interaction – Risks to Technicians and Crew The typical activities for operating and maintainin g the Ecochlor ® BWTS that present potential risks to technicians or other personnel are assesse d in this section. These tasks include normal system operation, system maintenance and chemical r efill operations. The areas for potential exposure are limited to the areas where the BWTS an d chemical storage tanks are located, where pipelines traverse, and where chemical re-supply op erations take place.

In this section we refer to ‘technicians’, who are trained Ecochlor personnel or properly trained representatives from distributors or service compan ies used by Ecochlor. Technicians or properly trained Ecochlor representatives are the o nly individuals who will work within close proximity to the BWTS, perform maintenance, or hand le chemicals related to the Ecochlor ® BWTS. As such, technicians are the population grou p that has the greatest potential for
exposure.

Occasionally, other individuals such as ship crew m embers, port staff, stevedores, or ship repair contractors may be working in the vicinity of the E cochlor ® BWTS. In this section, these persons are referred to as ‘other personnel’ or ‘sh ip’s crew’. The contact these personnel may have with the BWTS would be specific to the BWTS lo cation on the vessel and the work activities taking place in that location (i.e. carg o space vs. engine room vs. deck house). For example, the BWTS may be located in a designated ar ea of a cargo hold where various work tasks or cargo operations are performed. Simply wo rking within proximity to the BWTS would not lead to direct contact with the BWTS or chemica ls. Therefore, this subpopulation has a low potential for exposure and the BWTS does not pose u nacceptable risks to ship’s crew or other personnel who may perform work tasks nearby.

6.2.1.1 Normal System Operation Operation of the Ecochlor ® BWTS does not require technician or ship’s crew in volvement, unless the ship’s ballast system is manual in natur e and is not capable of providing electronic signals regarding the ballast system status. Even in such an installation, a crew member would only be required to push a remote ‘start’ button an d possibly adjust ballast system valves. In either case, the BWTS automatically delivers the pr eparation chemicals and the active substance, and no technicians or crew members are required to be at the location of the BWTS while in operation. The BWTS automatically starts, stops, a nd doses the correct amount of chlorine dioxide. At no time during the normal operation of the system are Ecochlor technicians or ship crew members required to handle chemicals.

With the exception of the vent lines on the precurs or chemical storage tanks, the BWTS is a closed system. Chemical tank vent lines are direct ed either to the atmosphere or to spaces with proper ventilation (also refer to the discussion in Section 3.0.8.2). The Ecochlor system does not give off fumes or gases during normal operation. H owever, a small amount of fumes may be displaced when the chemical storage tanks are refil led, and sufficient ventilation is necessary during these operations. See Section 6.2.1.2 below

.53

The system does not generate a significant level of noise that would pose hearing damage risks to technicians or other personnel.

6.3 RISKS TO HUMAN HEALTH

6.3.1 Identification of Chemicals of Potential Conc ern and Sources The chemicals of potential concern (COPC) related t o the Ecochlor ® BWTS are Purate ® , sulfuric acid, and chlorine dioxide. Purate ® (40% by weight sodium chlorate and 8% by weight hydrogen peroxide) and sulfuric acid (78%) are prep aration chemicals used to generate chlorine dioxide.

Although low levels of chlorite ion may persist in treated ballast water, no sources of direct contact or exposure to the by-product exist for tec hnicians or ship’s crew. Additionally, the chemical properties and modes of chlorite ion degra dation indicate that it will not persist in the environment or have the potential to bioaccumulate (refer to Section 2.3). As such there is no mechanism of transport that would allow primary or secondary exposure risks for technicians, ships crew, persons at the coast or seafood consume rs. Chlorite ion is not considered further in this human health risk assessment.

6.3.2 Exposure Assessment An exposure pathway describes the course that COPC take from a source to an individual. A complete exposure pathway consists of the following :

• A source of the chemical(s) of concern;

• An environmental medium (i.e. air) containing the c hemical(s) of concern;

• An exposure point or direct contact point with the contaminated medium (i.e. direct contact with the chemical(s)) or a release mechanis m for contact with a secondary medium (i.e. vaporization of chemicals); and

• An exposure route for chemical intake by an individ ual (i.e. inhalation).
The combination of all four components together mak es a complete exposure pathway. If one or more of the components is missing, the exposure pat hway is considered incomplete. Incomplete exposure pathways do not present potential human he alth hazards.

Areas for potential exposure are defined as areas w here both the COPC and human receptors may come in contact. The onboard areas, or sources of chemicals, with potential for exposure to Purate ® , sulfuric acid and chlorine dioxide are limited to the areas where the BWTS and chemical storage tanks are located, where pipelines traverse, and where chemical re-supply operations take place.

The potential media for exposure relating to the Ec ochlor ® BWTS that have been identified are direct contact with chemicals and air containing vo latiles of the COPC within enclosed ship spaces. Treated ballast water is not considered as a potential exposure medium to Purate ® and sulfuric acid because these substances are consumed in the chlorine dioxide generation reaction. Further, chlorine dioxide degradation behavior indi cates that chlorine dioxide will not persist in the environment, nor does it have the potential to bioaccumulate (refer to Section 2.3). Thus,54

there is no complete exposure pathway for contact w ith treated ballast water containing Purate ®

, sulfuric acid or chlorine dioxide for Ecochlor tech nicians, ships crew, persons at the coast, or seafood consumers. However, because chlorine dioxi de in solution readily volatilizes, a potentially complete exposure pathway for inhalatio n of chlorine dioxide from treated ballast water exists.

The populations with the greatest potential for exp osure are Ecochlor technicians, and to a lesser extent, ships crew and/or other personnel (see expl anation of those in this population group in Section 6.2.1). Technicians have a greater potenti al for exposure because they will work most closely with the BWTS (i.e. performing maintenance and chemical re-supply operations, etc.). Because ship’s crew will never be required to handl e chemicals during operation of the BWTS or be directly involved in chemical-handling operation s, the exposure potential for this population group is extremely low. To fulfill the components necessary for a complete exposure pathway, chemical exposure would only occur in the event of a pipeline or storage tank failure, or an emergency situation in the same space where ships c rew may be working. In this unlikely event, the most probable exposure route would be inhalatio n rather than direct chemical contact.

With the exception of the vent lines on the precurs or chemical storage tanks, the chemicals used with the BWTS are in a closed system. Chemical tan k vent lines are directed either to the atmosphere or to spaces with proper ventilation. F urther, ballast tank vents are directed to atmospheric conditions outside a ship. Thus, chlor ine dioxide that may volatilize from treated water within the ballast water tanks does not prese nt a complete inhalation exposure pathway. As such, with the exception of an emergency situati on, a complete exposure pathway for inhalation or direct chemical contact exposure rout es does not exist while the BWTS is in normal operation.

During routine system maintenance and chemical re-s upply operations chlorine dioxide would not be generated. Thus, these operations would onl y involve potential exposure to Purate ®
and/or sulfuric acid for Ecochlor technicians. Bas ed on this evaluation, potential exposure to chlorine dioxide could only occur for technicians d uring an emergency situation (i.e. pipeline failure). For ships crew, potential exposure to Pu rate ® , sulfuric acid and/or chlorine dioxide could only occur during an emergency situation invo lving the BWTS (i.e. storage tank or pipeline failure).

Emergency situations onboard that are not related t o the BWTS (i.e. ingress of water, fire on board) would not necessarily create completed chemi cal exposure pathways. For instance, if ingress of water onto the ship occurred, this would not necessarily alter the integrity of the chemical tanks and cause a tank or pipeline failure . Additionally, the BWTS is a closed system and water would not be able to enter the chemical t anks. Similarly, a fire onboard that is unrelated to the BWTS would not necessarily create a completed exposure pathway. This is because the chemical solutions are not flammable or explosive. Even if the fire is nearby causing the chemicals to heat, the vapors would be vented.

Additionally, the standard operating procedures tha t would be implemented in an emergency situation that is not related to the Ecochlor ® BWTS (i.e. ingress of water, fire onboard) are not changed as a result of the system being onboard.55

6.3.3 Potential Exposure Health Risks The components of Purate ® (sodium chlorate and hydrogen peroxide), as well a s sulfuric acid, are considered non-carcinogenic substances. Insuff icient data is available for classification of chlorine dioxide as a human carcinogen 8

.

Inhalation of Purate ® vapors and/or mists is irritating to the mucous me mbranes, and may cause nausea, headache and/or weakness. Inhalation expos ure can have an oxidizing effect, and oxidizes hemoglobin in the blood to methaemoglobine mia, causing a reduced ability to transport oxygen. This can lead to a lack of oxygen in body tissues. Inhalation of sulfuric acid mists or sprays can cau se pulmonary irritation, irritation of the mucous membranes, coughing and sore throat. Inhalation of high concentrations may cause respiratory tissue damage, causing lung disorders (chemical pne umonitis and pulmonary edema) and erosion of tooth enamel.

Chlorine dioxide is a strong, corrosive respiratory irritant, and the respiratory tract appears to the primary target of toxicity in human and animal stud ies 8 . Reported symptoms include cough, wheezing, headache, nausea, pulmonary edema and sho rtness of breath.

Direct chemical contact with Purate ® may cause moderate irritation to the skin, and can cause severe eye irritation, tearing and blurred vision, with irreversible corneal damage and possible blindness in instances of overexposure.

Direct chemical contact of sulfuric acid with the s kin or eyes can cause severe irritation, burns and permanent tissue damage. Absorption through th e skin is not anticipated to be a significant route of over-exposure.

Direct dermal contact with chlorine dioxide solutio n may cause redness and skin burns, and may cause severe eye irritation, pain, blurred vision, tearing corneal injury and burns.

6.3.4 Risk Characterization The exposure assessment identified potentially comp lete exposure pathways for Purate ® , sulfuric acid and chlorine dioxide with inhalation or direct chemical contact as the exposure routes. Exposure risks are present during system maintenanc e and chemical re-supply operations, or during emergency situations involving the BWTS.

The Ecochlor ® BWTS requires approximately 6 hours of preventativ e maintenance per year, and chemical re-supply operations will typically take p lace two - three times per year. Therefore, operations where potential exposure risks exist are limited in duration and frequency.

Preventing exposures and emergency situations begin s with proper engineering and construction of systems that are designed for use onboard ships. Thorough administrative measures, technician and crew training, engineering controls and standard operating procedures further mitigate potential exposures to the COPC. PPE worn by technicians greatly reduces the potential for the exposure pathways to be completed. For ins tance, during chemical re-supply operations, the required PPE consists of eye protection (chemic al goggles), and/or a face shield, along with chemical resistant clothing and gloves designed for use with Purate ® and sulfuric acid. These56

operations are only conducted in well-ventilated ar eas or with the use of appropriate engineering controls to prevent inhalation risks. However, in the event of an emergency situation where inhalation exposure may occur, respiratory protecti on devices would be added to the required PPE.

6.4 RISKS TO THE AQUATIC ENVIRONMENT With respect to risk, toxicity to aquatic organisms appears to be the most significant potential exposure for chlorine dioxide because it is not per sistent in the environment and is not expected to bioaccumulate or adsorb to sediments 2 . However, when the Ecochlor ® BWTS is utilized as directed by Ecochlor, the treated ballast water dis charge will contain undetectable concentrations of chlorine dioxide. Therefore, unacceptable risks to the aquatic environment from chlorine dioxide are not expected.

With respect to risk, toxicity to aquatic organisms appears to be the most significant potential exposure for chlorite ion because it is not persist ent in the environment and is not expected to bioaccumulate or adsorb to sediments 2 . The chlorite ion measured in treated ballast wat er ranges from <0.1 mg/L to 2.37 mg/L. Because treated balla st water may contain residual chlorite ion when discharged, a dilution to approximately 12% ha s been calculated to achieve the chronic NOEC for M. bahia to chlorite ion (see Section 5.2.1.1). The calcul ated dilution to 12% was based on toxicity tests done with the upper range o f chlorite ion measured in treated ballast water (2.35 mg/L), and with the chronic NOEC for M. bahia , which was identified as the species most sensitive to chlorite ion.

Additionally, dilution to 12% (v/v) is considered c onservative because none of the other species tested would require dilution of treated ballast wa ter to reach the chronic chlorite NOEC. For instance, the next most sensitive species tested ( A. affinis , chronic NOEC 13.8 mg/L) was almost two orders of magnitude less sensitive to chlorite.

Therefore, dilution to 12% (v/v) is considered high ly conservative and protective of aquatic organisms to ensure there are no unacceptable risks to the aquatic environment.

6.5 ASSESSMENT REPORT (G9: 4.3)

6.5.1 Overview of Data and Endpoints As constituents potentially present in ballast wate r treated with the Ecochlor ® BWTS, chlorine dioxide and chlorite ion were evaluated in regards to persistence, bioaccumulation, and toxicity. In regards to persistence, chlorine dioxide was rep orted to have a half-life of 3.9 minutes in freshwater 2 , and the half-life of chlorite ion in sea water wa s measured as <1 hour. The estimated log K ow values for chlorine dioxide and chlorite are -3.22 and -7.17 3 , respectively. These K ow values, the physical and chemical characteristics (i.e. highly soluble, non-organic), along with well-documented degradation behavior, in dicate that chlorine dioxide and chlorite ion would not be expected to bioaccumulate. In regards to toxicity, the lowest chronic NOEC was 0.09 mg/L and 0.18 mg/L for chlorine dioxide and ch lorite ion, respectively. Therefore, chlorine dioxide and chlorite ion do not meet the criteria t o be classified as PBT substances.57

In a toxicity evaluation of treated ballast water, the lowest acute LC50 was 37.7% (v/v) for Mysidopsis bahia and the lowest chronic EC50 was >81% (v/v) for Mytilus sp. (Tables T2.9 and T2.10). By calculation, these values compare well with the chlorite ion toxicity observed for M. bahia (Table T2.10 and Section 5.3.8). The evaluation o f treated ballast water toxicity resulted in a calculated dilution to 12% (v/v) to achieve th e chronic NOEC for M. bahia to chlorite ion. This dilution was derived using the upper limits of chlorite ion that may be present, as well as the most sensitive species in toxicity tests (see Secti on 6.4) to incorporate a sufficient safety margin.

Ecochlor has conducted a significant number of test s on various waters to determine the holding time necessary, and evaluate the effects of differi ng water conditions (i.e. organic load, pH, salinity, temperature). Although additional studie s are planned to increase the available data set for treated ballast water, Ecochlor is confident in the data that has been generated through laboratory analysis and onboard testing.

As presented in Sections 2.3.3 and 5.3.1, both chlo rine dioxide and chlorite ion are oxidizing agents that do not produce harmful organic by-produ cts. Additionally, chlorine dioxide degrades rapidly in marine and fresh waters, predominantly forming chlorite ion as a degradation byproduct 2 . Degradation of both substances is by abiotic mec hanisms and is predominantly a result of oxidative reactions.

When the Ecochlor ® BWTS is utilized as directed by Ecochlor, the conc entration of chlorine dioxide is expected to be at undetectable levels wh en treated ballast water is discharged. Thus, the predicted environmental concentration (PEC) for chlorine dioxide is 0 mg/L. Ion chromatographic analysis of ballast water treated w ith 5.0 mg/L of chlorine dioxide indicate chlorite ion concentrations ranging from <0.1 g/L t o 2.37 mg/L. Therefore, the PEC for chlorite ion in treated ballast water is <0.1 mg/L to 2.37 m g/L. This range is a result of the varied chlorite ion demand of different waters and factors such as organic load, pH and temperature that affect the decay rate. Section 2.0.3.2 discusses c hlorite ion demand / decay in greater detail.

The Ecochlor ® BWTS can safely and effectively treat ballast wate r for AIS to comply with the performance standards in Regulation D-2 of the Inte rnational Convention for the Control and Management of Ship’s Ballast Water and Sediments, a s well as standards proposed in the US Ballast Water Management Act of 2005 (Senate Bill S .363). Based on laboratory analysis and shipboard data of treated ballast water, no related adverse effects from the use of the Ecochlor ® BWTS to comply with the Convention can be reasonabl y anticipated. The level of uncertainty in the data supporting this opinion is low. Additiona l data continues to be collected on the Ecochlor ® BWTS, further increasing the confidence in the res ults obtained through various analyses.

The potential risks to the safety of ships, human h ealth and the environment are mitigated by engineering and constructing systems that are desig ned for use onboard ships, proper chemical production, dosing, storage and handling, as well a s thorough personnel training and use of PPE. The automatic dosing of chlorine dioxide treatment based on the amount of ballast water being brought onboard limits chlorine dioxide production, ensuring safe discharge of treated water to the environment. The substances used with the Ecoc hlor ® BWTS are not expected to persist in58

the environment or bioaccumulate, thereby presentin g no risks to resources (i.e. beaches, fisheries).

The active substance is generated on demand, applie d in situ, and is never stored onboard. After injection into the ballast water, the concentration of chlorine dioxide decays quickly (within than 24 hours). When used as directed, the ballast wate r treated with Ecochlor ® BWTS will have undetectable concentrations of chlorine dioxide at the time of discharge. Thus the PEC for chlorine dioxide is 0 mg/L. Therefore, a situation where the PEC/PNEC ratio is >1 at discharge is not anticipated. Further, no waste stream is cr eated during the treatment process.

6.5.2 Test Report Data Quality Test reports used in this application were from a v ariety of sources, including, but not limited to, OECD SIDS, Eka Chemicals (performed by independent laboratories), independent research, USEPA, and the National Toxicology Program. The re ports were evaluated to ensure that the data presented was generated by accredited laborato ries using accepted standard methodologies and laboratory practices. The data met acceptable confidence intervals (i.e. >95%), indicating a low level of uncertainty associated with the data. For example, the following is quoted text from one mammalian toxicity study used in the risk chara cterization (Eka Study 86-3112 5 ):

“Results of the inspections made by the Quality Ass urance Unit at BIO/dynamics, Inc. indicate that this study was conducted in complianc e with applicable United States Environmental Protection Agency’s Good Laboratory P ractice Standards and applicable Standard Operating Procedures. No significant devi ates were noted. Minor deviations may be include in the raw data”

The studies referenced in this application are list ed in the “Reference Documents” portion of the Table of Contents and are included in a complete co py of the application.

****

LIST OF TABLES

Table T2.1 – Overview of Chemical Identification Table T2.2 – Ecochlor Chlorine Dioxide Demand Study , 4oC Table T2.3 – Ecochlor Chlorine Dioxide Demand Study , 12oC Table T2.4 – Ecochlor Chlorine Dioxide Demand Study , 24oC Table T2.5 – Ecochlor Chlorite Ion Demand Study, 20 oC Table T2.6 – Chlorite Ion Dilution / Demand Study, New Jersey Water Table T2.7 – Chlorite Ion Dilution / Demand Study, Maryland Water Table T2.8 – Analysis of Ballast Water Treated Onbo ard the M/V Moku Pahu Table T2.9 – Overview of Acute Aquatic Toxicity Table T2.10 – Overview of Chronic Aquatic Toxicity Table T2.11 – Acute Mammalian Toxicity Data Table T2.12 – Skin, Eye and Dermal Effects Table T2.13 – Repeated-Dose Toxicity Table T2.14 – Chronic Mammalian Toxicity Table T2.15 – Physical and Chemical Properties Table T3.1 – List of BWTS Monitoring & Control Devi ces Table T3.2 – Eka Chlorine Dioxide Generator Operati onal Reliability Data Table T5.1 – PBT Criteria for Chlorine Dioxide & Ch lorite Ion Table T6.1 – Comparison of Corrosion Rates59 LIST OF FIGURES
Figure F2.1 – Example of Chlorine Dioxide Demand Cu rve, 4°C Figure F2.2 – Example of Chlorine Dioxide Demand Cu rve, 12°C Figure F2.3 – Example of Chlorine Dioxide Demand Cu rve, 24°C Figure F2.4 – Example of Chlorite Ion Demand Curve, Newark, NJ Water Figure F2.5 – Chlorite Ion Dilution / Demand Study, New Jersey Water Figure F2.6 – Chlorite Ion Dilution / Demand Study, Maryland Water Figure F3.1 – Photo of Full Scale Ecochlor ® BWTS Figure F3.2 – Ecochlor ® BWTS Process Flow Diagram Figure F6.1 – Salt Content and Water Corrosivity Figure F6.2 – Dissolved Oxygen and pH

REFERENCE DOCUMENTS

1 OECD SIDS SIAR, SIAM 11 (January 2001), UNEP Pub lications.
2 Review of the Environmental Fate and Effects of Chlorine Dioxide and Chlorite, Nautilus Environmental, 2007. 3 USEPA Reregistration Eligibility Decision (R ED) for Chlorine Dioxide and Sodium Chlorite (Case 4023), August 2006.
4 Concise International Chemical Assessment Do cument (CICADS) 37, Chlorine Dioxide (Gas), 2002. 5 Barrett, D.S. (1987) A Subchronic (3 Month) Oral Toxicity Study of Sodium Chlorate in the Rat v ia Gavage. 6 Barrett, D.S. (1987) A Subchronic (3 Month) Oral Toxicity Study in the Dog via Gavage Administration with Sodium Chlorate. 7 Scientific Committee on Consumer Products (S CCP), Opinion on Hydrogen Peroxide in Tooth Whitening Products, 2005. 8 USEPA Toxicological Review of Chlorine Dioxi de and Chlorite, September 2000. 9 NTP Technical Report on the Toxicology and C arcinogenesis Studies of Sodium Chlorate in F344/N Rats and B6C3F1 Mice (Drinking Water Studie s), 2005. NTP TR 517, NIH Publication No. 06-4457. 10 European Chemicals Bureau (2003) Hydrogen Per oxide Summary Risk Assessment Report, Special Publication I.03.148. 11 Smith, D.J., Anderson, R. C., Ellig, E.A., an d Larsen, G.L. (2005) Tissue Distribution, Eliminat ion, and Metabolism of Dietary Sodium [36Cl}Chlo rate in Beef Cattle. 12 Abdel-Rahman, M.S., Couri, D., and Bull, R.J. (1982) Metabolism and Pharmacokinetics of Alternat e Drinking Water Disinfectants. Environmental Health Perspectives, v46, pp19-23. 13 EPA Guidance Manual, Alternative Disinfectant s and Oxidants, Chlorine Dioxide, 1999 (http://www.epa.gov/safewater/mdbp/pdf/alte r/chapt_4.pdf). 14 Simpson, G.D., Miller, R.F., Laxton, G.D., Cl ements, W.R., A Focus on Chlorine Dioxide: The “Ideal” Biocide. 15 Mosser, Mark L., Sermatech International Inc. , September 15, 2005. 16 The Sulphur Institute Online, Glossary of Ter ms (http://www.sulphurinstitute.org/webarticle s/anmviewer.asp?a=109&z=30).
17 Heidersbach, Bob; Dr. Rust, Inc.; Ballast Wat er Corrosion Rates Using the Ecochlor ® Ballast Water Treatment System, May 2007. 18 Corrosion Analysis Data Report, Metal Samples , Co., 2005. 19 Physical and Chemical Characteristics of Pura te ® , Case Consulting Laboratories, 2000. 20 Chlorine Dioxide and Chlorite Toxicological P rofile, Agency for Toxic Substances and Disease Registry (http://www.atsdr.cdc.gov/toxprofi les/tp160-c4.pdf).

****