Critical Review of a 

Ballast Water Biocides Treatment Demonstration Project 

Using Copper and Sodium Hypochlorite

 (A Science Report to Governor John Engler)

 Prepared by 

 Michigan Environmental Science Board 

 Ballast Water Biocides Investigation Panel 

MICHIGAN ENVIRONMENTAL SCIENCE BOARD 

 CONSTITUTION HALL, 5TH FLOOR SOUTH 

 525 WEST ALLEGAN STREET 

P.O. BOX 30680 

 LANSING, MICHIGAN 48909-8180 

SEPTEMBER 2002 
 MICHIGAN ENVIRONMENTAL SCIENCE BOARD

 Ballast Water Biocides Investigation Panel

John A. Gracki, Ph.D. .......................(Grand Valley State University)....................................Chair 

Richard A. Everett, Ph.D. .........................(U.S. Coast Guard) ......................... Panel Member 

Harvey Hack, Ph.D. ...................(Northrop Grumman Corporation, Oceanic Systems)... Panel Member 

Peter F. Landrum, Ph.D. .................(U.S. Department of Commerce, NOAA) ............ Panel Member 

David T. Long, Ph.D. ........................(Michigan State University)....................... Panel Member 

Bette J. Premo, Ph.D. .....................(White Water Associates, Inc) ...................... Panel Member 

Stephen C. Raaymakers, B.S.C. .....(International Maritime Organization) ................. Panel Member 

Gregory A. Stapleton M.S., P.E. ...(U.S. Environmental Protection Agency)................ Panel Member 

Keith G. Harrison, M.A., R.S., Cert. Ecol. ..(State of Michigan)...................Ex. Officio Member 

 MICHIGAN ENVIRONMENTAL SCIENCE BOARD

Lawrence J. Fischer, Ph.D. .........................................................................................Chair 

Raymond Y. Demers, M.D. ......................................................................... Board Member 

John A. Gracki, Ph.D. ................................................................................. Board Member 

Ralph H. Kummler, Ph.D. ............................................................................ Board Member

David T. Long, Ph.D. ................................................................................... Board Member 

Ronald H. Olsen, Ph.D. ............................................................................... Board Member 

Bette J. Premo, Ph.D. .................................................................................. Board Member 

Eileen O. van Ravenswaay, Ph.D. ............................................................. Board Member 

George T. Wolff, Ph.D. ................................................................................ Board Member 

Keith G. Harrison, M.A., R.S., Cert. Ecol. ............................................Executive Director 

MICHIGAN DEPARTMENT OF ENVIRONMENTAL QUALITY

 OFFICE OF SPECIAL ENVIRONMENTAL PROJECTS SUPPORT STAFF

Keith G. Harrison, M.A., R.S., Cert. Ecol. .............................................................. Director 

Vacant ............................................................................................. Environmental Analyst 

Sharon Picard ....................................................................................... State Sites Analyst 

Katherine S. Tetzlaff ..........................................................................................Accountant 

Linda V. Albro Sparks ........................................................................ Executive Secretary 

Vacant ........................................................................................... Graduate Student Intern 

 Michigan Environmental Science Board 

 Constitution Hall, 5th Floor South 

 525 West Allegan Street 

P.O. Box 30680 

 Lansing, Michigan 48909-8180 

Telephone: 517-373-4960 

Fax: 517-373-6492 

 E-Mail: mesb@michigan.gov 

 Internet: <http://www.michigan.gov/mesb> 
Critical Review of a 

Ballast Water Biocides Treatment Demonstration Project 

Using Copper and Sodium Hypochlorite

 

 (A Science Report to Governor John Engler) 

Prepared by 

 Michigan Environmental Science Board 

 Ballast Water Biocides Investigation Panel

 

MICHIGAN ENVIRONMENTAL SCIENCE BOARD 

 CONSTITUTION HALL, 5TH FLOOR SOUTH 

 525 WEST ALLEGAN STREET 

P.O. BOX 30680 

 LANSING, MICHIGAN 48909-8180 

 

SEPTEMBER 2002 

 (FIRST PRINTING) 
ii

 Copyright © 2002 by the Michigan Environmental Science Board 

 State of Michigan, Constitution Hall, 5th Floor South 

525 West Allegan Street, P.O. Box 30680 

 Lansing, Michigan 48909-8180 

 All Rights Reserved 

Manufactured in the United States of America 

 Copies of this report may be obtained free of charge by either 

 writing to the Michigan Environmental Science Board or 

 downloading from the Michigan Environmental Science Board’s Home Page at: 

 http://www.michigan.gov/mesb

 

 1st Printing (September 2002): 400 Copies $528.00 

 (Cost per Copy: $1.32) 

 Printed by Authority of Executive Orders 1992-19 and 1997-3 

Correct Report Citation:

Gracki, J.A., R.A. Everett, H. Hack, P.F. Landrum, D.T. Long, B.J. Premo, S.C. Raaymakers, G.A. Stapleton and 

K.G. Harrison. 2002. Critical Review of a Ballast Water Biocides Treatment Demonstration Project 

Using Copper and Sodium Hypochlorite, September 2002. Michigan Environmental Science Board, 

Lansing. xii + 30p. 
iii

TABLE OF CONTENTS 

 Page 

Major Findings and Conclusions ............................................................................................................ vii 

Introduction ................................................................................................................................................. 1 

Charge to the Michigan Environmental Science Board.......................................................................... 2 

Overview of the Biocides Study ................................................................................................................ 3 

 Shipboard Toxicity Tests..................................................................................................................... 3 

 Laboratory Toxicity Tests.................................................................................................................... 3 

 Laboratory Corrosion Tests ................................................................................................................ 4 

 Summary of Study Conclusions ......................................................................................................... 4 

Michigan Environmental Science Board Critique.................................................................................... 5 

 Shipboard Toxicology Testing Protocol ............................................................................................ 5 

 Laboratory Toxicology Testing Protocol ........................................................................................... 7 

 Impact of Sediment .............................................................................................................................. 8 

 Biocide Discharge into the Great Lakes. ........................................................................................... 9 

 Laboratory Corrosion Testing Protocol. .......................................................................................... 10 

 

Conclusions............................................................................................................................................... 11 

 Copper Ion Biocide Efficacy and Discharge Concentrations......................................................... 11 

 Sodium Hypochlorite Biocide Efficacy and Discharge Concentrations....................................... 12 

 Impact of Biocides on Ballast Tank Corrosion................................................................................ 13

References Cited....................................................................................................................................... 15 

Appendix 1. Executive Summary, [Draft] Final Report: Ballast Water Treatment Evaluation 

 Using Copper and Sodium Hypochlorite as Ballast Water Biocides......................... 19 

Appendix 2. April 10, 2002 Correspondence to the Michigan Environmental Science 

 Board from Governor John Engler................................................................................ 25 

v 

 PREFACE 

Michigan Environmental Science Board

The Michigan Environmental Science Board (MESB) was created by Governor John Engler by 

Executive Order 1992-19 on August 6, 1992. The MESB is charged with advising the Governor, the 

Natural Resources Commission, the Michigan Department of Natural Resources and other state 

agencies, as directed by the Governor, on matters affecting the protection and management of 

Michigan's environment and natural resources. The MESB consists of nine members and an 

executive director, appointed by the Governor, who have expertise in one or more of the following 

areas: engineering, ecological sciences, economics, chemistry, physics, biological sciences, human 

medicine, statistics, risk assessment, geology, and other disciplines as necessary. Upon the 

request of the Governor to review a particular issue, a panel, consisting of MESB members with 

relevant expertise, is convened to evaluate and provide recommendations on the issue. The MESB 

is neither a state policy body nor an advocate for or against any particular environmental or public 

health concern. 

 Dr. Lawrence J. Fischer Dr. Ronald H. Olsen 

 MESB Chairperson MESB Member 

 Michigan State University University of Michigan 

 Dr. Raymond Y. Demers Dr. Bette J. Premo 

 MESB Member MESB Member 

 Henry Ford Health System White Water Associates, Inc. 

 Dr. John A. Gracki Dr. Eileen O. van Ravenswaay 

 MESB Member MESB Member 

 Grand Valley State University Michigan State University 

 Dr. Ralph H. Kummler Dr. George T. Wolff 

 MESB Member MESB Member 

 Wayne State University General Motors 

 Dr. David T. Long Mr. Keith G. Harrison 

 MESB Member MESB Executive Director 

 Michigan State University State of Michigan 

vii 

Critical Review of a Ballast Water Biocide Treatment Demonstration Project 

Using Copper and Sodium Hypochlorite

 

Major Findings and Conclusions 

Over 160 nonindigenous aquatic nuisance species (ANS) of plants and animals have been introduced 

into the Great Lakes Basin since the 1800s. Of these, more than one-third of the known Great Lakes 

ANS have been introduced in the last half of the 20th Century, with the greatest number of the 

introductions coinciding with the expansion of the St. Lawrence Seaway in 1959. Seventy percent of the 

ANS discovered since 1985 in the Great Lakes are native to fresh and brackish waters of the PontoCaspian region (Black, Caspian and Azov Seas) in Eurasia. The introduction of ANS has played a major 

role in modifying aquatic ecosystems within the Great Lakes Basin. The primary route of ANS entry into 

the Great Lakes has been through ballast water exchange from ocean-going ships. Although federal law 

mandates open water exchange to help reduce the risk of ANS found in ballast tanks and sediments, it 

does not ensure protection of the Great Lakes since many older and larger vessels cannot safely execute 

open water exchange and it does not address ballast water exchange that takes place on ships between 

Great Lakes ports. 

In May 2001, the Michigan Department of Environmental Quality (MDEQ) issued a request for proposals 

for shipboard testing of two ballast water tank biocides, hypochlorite and copper ion, to determine their 

effectiveness against ANS. Fleet Technology Ltd. of Kanata, Ontario and ESG International of Guelph, 

Ontario was selected as the prime and subcontractors, respectively. The final draft report of the 

demonstration project (Study), entitled Ballast Water Treatment Evaluation Using Copper and Sodium 

Hypochlorite as Ballast Water Biocides was completed in April 2002. On April 10, 2002, Governor John 

Engler requested that the Michigan Environmental Science Board (MESB) review the final draft Study and 

evaluate the scientific validity of the conclusions reached regarding the efficacy of the two biocides 

evaluated; corrosivity to ballast tanks resulting from the two biocides; and discharge concentrations for 

each biocide needed to meet regulatory standards. Major findings and conclusions of the MESB are 

summarized below. 

♦ Copper Ion Biocide. Copper as an ion (e.g., Cu2+) is a naturally occurring chemical in the 

environment and necessary for various metabolic processes. At high concentrations, copper is toxic and 

is used to control algae and bacteria in swimming pools and lakes. Because of its toxic effects on biota 

such as fish, copper discharge to surface water is of concern. If a copper biocide treatment is used for 

ballast discharge, then this discharge water would most likely need to be regulated. The Study’s test 

results demonstrated that the copper ion biocide was only 33 percent effective at 167 parts per billion 

(ppb) in freshwater and 70 percent effective at 68 ppb in reducing bacteria in freshwater and simulated 

seawater experiments, respectively. These results suggest that at the concentrations tested, copper 

treatment was not effective. In order to be effective, even higher concentrations of copper would be 

needed, which would result in the further exceedance of the range of theoretical allowable discharge 

concentration levels (2 ppb to 48 ppb) determined by the Study for the Great Lakes jurisdictions. 

In addition to potential limits on copper concentrations that could be used, the efficacy of copper in killing 

biota ballast water is influenced by the natural geochemical behavior of copper in the environment. For 

example, copper is a particle reactive chemical. This means that it will tend to be adsorbed to sediments, 

whether suspended or settled. Consequently, the presence of sediment in the ballast tank would reduce 

the efficacy of copper as a biocide and higher concentrations of copper would need to be used compared 

to water in the absence of the sediment. This issue was not addressed in the Study. 

The behavior and toxic effects of copper in water also are altered by natural processes, such as the 

formation of ion pairs in solution. In solution solutes, copper (Cu2+) can bond with other solutes, such as 

bicarbonate (HCO3

-

), to form new dissolve chemical species known as an ion pair or complex. The 

formation of this ion pair decreases the toxicity of a copper. Since copper in solution is particularly 

influenced by the presence of dissolved organic matter, bicarbonate, and carbonate in water, changes in 

the relative abundances in these solutes might necessitate different amounts of copper concentrations 
viii 

needed as a biocide. This point is important to consider when interpreting the results of the Study’s 

simulated seawater experiments since, if the simulated solution did not contain proper amounts of 

solutes, such as sulfate and bicarbonate, the experimental results observed in the Study might not 

represent the true behavior of copper. 

Copper ion concentrations in water of 0.02 to 0.05 ppm can cause severe corrosion of aluminum. For this 

reason, discharge of copper ion treated water from ballast tanks could cause significant corrosion of 

nearby aluminum-hulled boats and aluminum structures. It would be important to evaluate this issue 

further prior to proceeding with any additional consideration of copper ion as a ballast water biocide. 

In summary, the Study’s toxicity data, as a whole, suggest that in sufficiently high concentrations, copper 

ion could be an effective biocide. However, at the concentrations needed to achieve the desired 

effectiveness, the level would be far too high to be discharged into the Great Lakes. Given this, and in 

the absence of any known neutralizing agent that would allow copper to be safely discharged into the 

Great Lakes, the MESB Panel concludes that copper ion cannot be considered to be a viable ballast 

water biocide alternative at this time. 

♦Sodium Hypochlorite Biocide. The Study’s conclusions regarding the effectiveness of sodium 

hypochlorite as a viable ballast water biocide alternative from the shipboard and laboratory toxicity tests 

are limited and can only be considered preliminary at best. However, despite the problems outlined in 

this critique regarding the testing protocols used, the MESB Panel suggests that the use of sodium 

hypochlorite as a ballast water biocide can have a high degree of efficacy when treating the majority of 

organisms that were tested in the Study, assuming sufficient active hypochlorite concentration can be 

attained to account for sediment loads from both suspended and deposited material. Considerable more 

work will need to be conducted before any definitive statement regarding its efficacy within an actual 

ballast water tank environment can be made. In particular, well planned and controlled toxicity tests need 

to be conducted that will evaluate the biocide’s effectiveness on both benthic and resting stages of ANS 

in the presence of both suspended and bottom sediment similar to that found in ballast water tanks. Also, 

a mechanism needs to be developed and a careful analysis needs to be conducted that will determine 

how much chlorine remains available over time in the ballast tank in order to: (1) ensure the presence of 

an effective concentration of the biocide at the time when it is needed, and (2) allow for a determination to 

be made as to how much neutralizing compound would be needed for dechlorination prior to ballast water 

discharge. 

♦Biocide Discharge Concentrations. There exists no state or federal permitting requirements 

specifically for ballast water discharges and ballast water discharges are exempted from point-source 

discharge regulations. However, discharges of ballast water treated with sodium hypochlorite still would 

need to be of such quality so as to protect the designated uses of receiving waters. While the Study did 

attempt to address the issue of discharge of treated ballast water, the MESB Panel concludes that 

insufficient information (too few tests and lack of data as to what requirements would need to be met 

throughout the Great Lakes jurisdictions), was provided to definitively address the question regarding if 

such discharges could be safely and legally discharged into Great Lakes waters. Additional studies 

involving the use of actual ballast water treated with the biocide and a clear indication as to what would 

be required by the various U.S. and Canadian Great Lakes jurisdictions in order to meet Great Lakes 

water quality standards would be useful. 

The MESB Panel also concludes that biocide treatment in the absence of some other mechanism to 

address ballast water sediment, such as filtration, will result in an incomplete elimination of ANS. Future 

studies will need to address this problem by investigating the efficacy and the practicality of shipboard 

use of combined treatment methodologies. 

♦ Biocide Corrosivity. The biocide corrosion tests that were conducted in the Study were of too short a 

duration to allow prediction of long-term corrosion rates or coating degradation rates. Corrosion is not 

always constant over time, and, unless the time-dependence of corrosion rate is known, it is not possible 
ix 

to extrapolate data from short-term tests to predict long-term performance. In particular, coating 

degradation typically has an incubation time when the corrosive constituents are diffusing through the 

coating to the base metal underneath. For ballast water tank coatings, this incubation time can be many 

months. In addition, the tests should have used natural seawater and should have included cathodic 

protection for some of the exposures to better simulate the actual ballast water tank environment. 

The hypochlorous acid that is proposed as a biocide is an oxidant and can increase the corrosion of steel 

in water if present in quantities similar to the other oxidant in seawater, dissolved oxygen. The effect may 

become noticeable at concentrations of 1 part per million (ppm) or more if the kinetics of the reactions is 

favorable. Just as important, this oxidant may negatively affect the performance of paint systems on 

steel. Therefore, a new corrosion test would need to be conducted to determine the magnitude of these 

effects. 

Based on the information presented in the Study, the MESB is unable to reach definitive conclusions 

regarding the nature and extent of detrimental corrosion effects of either biocide on ballast tank structural 

integrity. Additional, better designed and longer duration tests will be needed to more fully evaluate this 

concern. 

Critical Review of a 

 Ballast Water Biocide Treatment Demonstration Project 

 Using Copper and Sodium Hypochlorite 

 (A Science Report to Governor John Engler)

1 

Introduction 

Over 160 nonindigenous aquatic nuisance species (ANS) of plants and animals have 

been introduced into the Great Lakes Basin since the 1800s. Of these, more than onethird of the known Great Lakes ANS have been introduced in the last half of the 20th 

Century, with the greatest number of the introductions coinciding with the expansion of 

the St. Lawrence Seaway in 1959 (Ricciardi, 2001; Mills et al., 1993). According to 

Ricciardi and MacIsaac (2000), 70 percent of the ANS discovered since 1985 in the 

Great Lakes are native to fresh and brackish waters of the Ponto-Caspian region (Black, 

Caspian and Azov Seas) in Eurasia. 

The introduction of ANS, such as the sea lamprey (Petromyzon marinus), zebra mussel 

(Dreissena polymorpha), European ruffe (Gymnocephalus cernuus), tubenose goby 

(Proterorhinus marmoratus), round goby (Neogobius melanostomus), spiny water-flea 

(Bythotrephes cederstroemi), curly leaf pondweed (Potamogeton crispus), and Eurasian 

water milfoil (Myriophyllus spicatum), has played a major role in modifying aquatic 

ecosystems within the Great Lakes Basin (Ricciardi, Neves, and Rasmussen, 1998; 

MacIsaac, 1996; Mills et al., 1993; Keast, 1984; Coffey and McNabb, 1974). Freed from 

natural competitors, predators, parasites, pathogens, and other factors that regulate the 

ANS populations in their native environments, ANS can grow at or near their potential 

exponential growth rate and out-compete the native species for food and/or habitat 

(Mack et al., 2000). Consequently, many of the ANS have severely disrupted Great 

Lakes native plant and animal species populations and ecosystem functions (Mack et

al., 2000; Lubomudrov, Moll and Parsons, 1997; Allan and Flecker, 1993). 

The primary route of ANS entry into the Great Lakes has been through ballast water 

exchange from ocean-going ships (Parsons and Harkins, 2000; Mills et al., 1993). A 

ballasted ocean freighter entering the Great Lakes typically carries three million liters of 

ballast water, which is discharged before taking on cargo. According to Locke et al.

(1993), approximately 800 million liters of ballast water are released into the system 

every year. Pursuant to the federal Nonindigenous Aquatic Nuisance Prevention and 

Control Act of 1990, as amended (NANPCA, 1990), some ships are now required to 

exchange their ballast water at sea, flushing out organisms and raising the salinity of the 

ballast water to kill freshwater organisms that might remain alive in the ballast tank. 

Although open water exchange helps reduce the risk of ANS found in ballast tanks and 

sediments, it does not ensure protection of the Great Lakes since for many older and 

larger vessels, open water exchange may not be feasible or safely executed (Designers 

& Planners, Inc and Herbert Engineering Corp., 1998; Ryle, 1995). In addition, current 

federal regulations apply only to those vessels that claim to be carrying ballast on board 

(BOB). Vessels that enter with no ballast on board (NOBOB) are exempt from the 

regulations. NOBOB ships can still contain substantial amounts of unpumpable water 

and sediment in their ballast tanks and, therefore, harbor adult organisms, 

dinonflagellate cysts, and diatom resting spores. Consequently, other control methods 

such as filtration, heat, ultraviolet light, and a variety of different types of biocides 

treatments also are being studied in an effort to find an effective method or combination 
2 

of methods to control ANS (Oemcke, 1999; Lubomudrov, Moll and Parsons, 1997; 

Lloyd’s Register Engineering Services, 1995; Laughton, Moran and Brown, 1992). 

In April 2000, the Michigan Department of Environmental Quality (MDEQ) convened a 

workgroup of technical experts from international and domestic shipping industries, and 

the U.S. Coast Guard to examine potential ballast water treatments including 

technologies, management practices, and biocides. The Ballast Water Working Group 

(BWWG) focused on what was currently available and practical, and what could be put 

into use as an interim measure while other related research continued. The BWWG 

concluded that the only currently available methods for dealing with the problem were 

management practices and biocides. The BWWG defined a currently available method

as: (1) not needing extensive research to establish the efficacy of the biocide, (2) not 

needing extensive ship retrofitting, and (3) not requiring any shore-side facilities. 

In May 2000, the BWWG concluded that: (1) management practices and biocides are 

the only two methods currently available to minimize the introduction of ANS, (2) 

hypochlorite and glutaraldehyde are potentially currently available ballast water 

biocides, and (3) shipboard field-testing of the biocides should be carried out as soon as 

possible. In February 2001, the BWWG recommended that a third biocide, copper ion, 

be added to the list of potential biocides. In May 2001, the MDEQ issued a request for 

proposals for shipboard biocide testing of hypochlorite and copper ion (a test of 

glutaraldehyde was proceeding under a separate grant). FedNav, a major transoceanic 

shipping company plying the Great Lakes, agreed to provide a ship (Federal Yukon) for 

the experimental work. Fleet Technology Ltd. of Kanata, Ontario, was selected as the 

prime contractor. The subcontractor was ESG International of Guelph, Ontario. The 

final draft report of the demonstration project (Study), entitled Ballast Water Treatment 

Evaluation Using Copper and Sodium Hypochlorite as Ballast Water Biocides (BMT 

Fleet Technology, Ltd. and ESG International, Inc. 2002, see Appendix 1), was 

completed in April 2002. 

Charge to the Michigan Environmental Science Board 

On April 10, 2002, Governor Engler (Engler, 2002) requested that the Michigan 

Environmental Science Board (MESB) review the final draft Study and evaluate the 

scientific validity of the conclusions reached regarding the: 

1. Efficacy of the two biocides evaluated; 

2. Corrosivity to ballast tanks resulting from the two biocides; and 

3. Discharge concentrations for each biocide needed to meet regulatory 

 standards (see Appendix 2). 

On April 14, 2002, a Ballast Water Biocides Investigation Panel (Panel), composed of 

four MESB members and five guest scientists, was formed to begin the investigation. 

The investigation consisted of an initial independent review of the Study by the Panel 
3 

members and a meeting (May 29, 2002) of the Panel, at which testimony and Study’s 

supportive documentation were presented and discussed (Harrison, 2002). 

Overview of the Biocides Study 

The Study was comprised of three parts: (1) a shipboard demonstration on board the 

Federal Yukon, (2) toxicology testing in a biological laboratory, and (3) corrosion testing 

in the materials laboratory (see Attachment 1). 

Shipboard Toxicity Tests. The purpose of the field demonstration portion of the Study 

was to examine the shipboard application of the two biocides and assess the efficacy of 

treatment on a single typical voyage, and to further determine whether the application of 

biocides adversely affects the real-life operations of the ship. The Study was not 

allowed to interfere with the commercial operations of the ship and certain on-site 

modifications to the experimental plan were necessary to accommodate the local 

biological conditions and engineering difficulties encountered. The tests were 

conducted on the deck of the ship using 55-gallon plastic barrels as test chambers. 

Additionally, a deck-mounted decant tank (a metal tank typically reserved for capturing 

cargo wash water prior to discharge) was modified and coated with paint used in the 

ballast tanks for additional hypochlorite tests. 

A typical voyage profile for a ship on international trade into the Great Lakes consists of 

loading cargo overseas and transiting the ocean as a NOBOB. On arrival at a Great 

Lakes port, the ship discharges its cargo and takes on ballast to transit to a second 

Great Lakes port. Here, the ship will discharge that ballast and take on an out-bound 

cargo. The shipboard demonstration was conducted during one such typical 

international voyage to four ports: 

• Coastal Port #1 (ocean saltwater port): Cargo was offloaded and ballast 

water taken on. 

• Coastal Port #2 (ocean saltwater port): Cargo was taken on and ballast 

water discharged, creating a NOBOB condition. 

• Great Lakes Port #1 (Great Lakes freshwater port): Cargo was off-loaded 

and ballast water taken on. 

• Great Lakes Port #2 (Great Lakes freshwater port): Cargo was taken on 

and ballast water discharged. 

Laboratory Toxicity Tests. The purpose of the laboratory toxicity testing portion of the 

Study was to quantify the efficacy of the biocides as it relates to the treatment of 

organisms in ballast water. The toxicity testing was conducted on freshwater and 

saltwater fish, invertebrates, algae, and bacteria. In addition, the toxicity of the biocides 

to selected ANS resting stages was evaluated. In certain instances, the toxicity of the 

biocides was tested in both laboratory and ballast water collected from the ship. A 

limited number of tests were conducted with and without the presence of clean control 

sediment for characterizing the effect of sediment on biocide efficacy. 
4 

Laboratory Corrosion Tests. The purpose of the laboratory corrosion testing portion 

of the Study was to examine the possible detrimental effects that the addition of biocide 

to ballast water may have on the structural integrity of the vessel. The effects of 

biocide-treated water on coating systems and base metals typically used in the 

construction of ships ballast tanks were investigated in a specially adapted corrosion 

tank. The different conditions of metal exposure within a ballast tank to ballast water 

(e.g., fully submerged, a splash zone or area of periodic immersion, and damp spaces) 

were simulated along with a “buried” experiment to show the effects on structure 

covered with sediment. The experiment used an accelerated corrosion testing concept 

to compare the effects of adding biocide to both fresh and saltwater. Corrosion tests 

were conducted on bare metal coupons, metal coupons coated with typical marine 

coating systems, and coated metal coupons that were scribed through the paint 

thickness to examine the effects of coating damage. 

Summary of Study Conclusions. Two shipboard ballast water biocide treatment trials 

conducted during a typical saltwater and freshwater voyage indicate that sodium 

hypochlorite (dosed to a residual of approximately 10 parts per million - ppm) 

significantly reduced (>90%) ambient zooplankton and bacteria levels relative to the 

controls after a two-hour treatment. In freshwater trials, copper ion treatment (<0.2 

ppm) was capable of reducing ambient zooplankton levels greater than 30 percent 

relative to the control. For both biocides applied at these levels, numerous organisms 

were capable of surviving treatment in settled sediments. 

Laboratory biocide toxicity tests conducted on freshwater and saltwater fish, 

invertebrates, algae, and bacteria, in test conditions that simulate those in a ballast tank 

showed that sodium hypochlorite was effective (i.e., achieved LC99 – the lethal 

concentration of substance that results in 99% mortality in a population) with the 

majority of species tested at less than a total residual chlorine of 10 ppm. Higher 

sodium hypochlorite levels were required to kill encysted life stages. The LC99 and EC99

(the effective concentration of a substance that results in 99% growth reduction, 

hatchability, or mortality in a population) values of the majority of species tested were at 

total copper levels below 200 ppm. The encysted life stages of certain test organisms 

were not killed at higher total copper levels. The presence of high levels of sediment 

negatively impacted the efficacy of both biocides. 

Accelerated (short-term) corrosion tests conducted on bare, coated, and scribed metal 

coupons under a variety of conditions (e.g., fully submerged, periodic immersion, damp 

spaces, and buried in simulated sediment) in saltwater and freshwater suggests that 

coupons exposed to sodium hypochlorite tend to experience slightly more corrosion and 

paint damage than the control samples; however, the effect is not quantifiable in terms 

of metal life expectancy from the analysis. No failures were observed in any unscribed 

coating system due to the presence of sodium hypochlorite. Short-term corrosion tests 

in solutions containing copper suggest that in the aggressive corrosion environment of 

salt water and periodic immersion, there is a slight increase in corrosion, but there were 

no increases in coating failures. 
5 

Michigan Environmental Science Board Critique 

The following MESB critique addresses concerns regarding the general experimental 

protocols used and conclusions reached in the Study. The critique focuses on sodium 

hypochlorite, although most of the methodological and interpretation concerns also 

apply to copper ion. 

Shipboard Toxicology Testing Protocol. In general, the MESB Panel found that the 

shipboard experimental design was not clear and was further complicated by the 

following issues: 

1. The distribution of treatments among container types was unbalanced within 

and between biocide and water types, with a lack of replication for some 

containers; 

2. The source and chemical make-up of sediments used was different between 

freshwater and seawater trials. This difference confounds the ability to 

ascribe differences in efficacy between the source waters to differential 

activities of the chemicals alone; 

3. The source of water was different between treatments, controls, and water 

sources. Some containers were filled through fire mains, thus bypassing 

ballast tanks, while others were filled from ballast tanks. This difference 

confounds the ability to ascribe differences solely to the presence of the 

biocide, or to compare among combinations of biocides and water types 

(fresh or salt); 

4. Physical conditions, as indicated by the amounts of suspended material 

present, were different between decant tanks and 55-gallon barrels; 

5. The methods for dosing hypochlorite to the decant tanks and 55-gallon 

barrels were not provided but were evidently different from that used to dose 

the copper ion. The former two types of containers were dosed after they 

were filled with water while the latter were dosed during filling of ballast tanks; 

and 

6. There is confusion regarding where the efficacy tests were conducted (e.g., in 

the decant tanks and 55-gallon barrels, or in 20-liter buckets using dosed 

water drawn from the tanks/barrels and organisms collected from the intake 

water/plankton tows). 

In addition to the problems with the experimental design, many of the specifics for the 

methods used in the shipboard tests were missing, including such critical items as 

methods of collection and addition of organisms to test chambers, number of samples 

per container, procedures for handling samples, and methods for calculating and 

comparing data. 
6 

Sediment chlorine demand was found to be a major issue that had to be adjusted for to 

provide appropriate target loads. The method for adjusting for the chlorine demand of 

the suspended sediment was not provided. The amount of sediment added to the test 

tanks was one percent on a volume-to-volume basis. The justification for the amount 

and the type of sediments used in the test should have been included in the Study 

based on the range of sediment quantity and type expected. 

The quantitative toxicology for the shipboard tests focused solely on pelagic organisms, 

while the data for the benthic organisms were circumstantial. It was clear from the 

Study that an effective dose would need to have been larger than the 10 ppm employed 

in the Study based on the presence of cysts and live benthic organisms found in the 

sediment. Recent work at the Great Lakes Environmental Research Laboratory 

(Landrum, 2002) indicates that concentrations in excess of 1,000 ppm would be 

required to be effective for sediment dwelling organisms in order to account for the 

chlorine demand of the sediment. 

Additional organisms from the local area had to be added to the shipboard test tanks to 

ensure that there were sufficient numbers to detect a response. There was nothing in 

the Study protocols to indicate how this was done. In addition, there was no testing of 

the health of the collected organisms to allow for comparison to the laboratory data. The 

tests were only performed with pelagic organisms and the exposures were done with a 

sub-sample of the water of unknown volume. It was not clear if the number of 

organisms at the end of the exposure was compared relative to controls or relative to 

t=0 for each tank. The Study indicated that the 55-gallon barrels from the copper ion 

test served as controls for the hypochlorite test; however, it was not clear whether these 

were performed at the same time using the same ballast water. Additional detail in the 

protocols regarding this issue could not be found in the Study. The protocols suggest 

that there would be an n of 4 for treatments and n of 2 for controls except for the decant 

tank, but the number of replicates and the data for both treatment and control tanks 

were not provided. 

The Study provides data suggesting 90 to 96 percent declines in the zooplankton on 

exposure to hypochlorite, but the method for determining these values was not 

provided. Because of the absence of the supporting information, it is not possible to be 

certain about the validity of these values. There was an indication in the Study that 

significant numbers of organisms could not be recovered at the end of the trials. It was 

not clear, however, if this was just for the treatments or also for the controls. 

The temperature of the shipboard tests varied from 12 to 20 degrees centigrade (o

C), 

but the laboratory tests were performed at 15oC. The impact of the temperature on the 

toxicity testing was not evaluated. Changes in temperature will affect both the 

degradation of the hypochlorite and the response of the organisms to the toxicant. While 

this does not affect the shipboard test results directly, it does make the setting of a 

toxicant dose from laboratory data problematic. 
7 

Finally, the conditions that existed the Study’s decant tanks and 55-gallon barrels 

cannot be considered identical to what would be expected to exist in the ballast tanks, 

and the dosing procedures used in the Study for hypochlorite and copper ion biocides 

cannot be considered as being what would be needed for actual ballast tank 

disinfection. Given the inability of the Study to duplicate ballast tank structure and the 

complications of mixing in an actual ballast tank environment, the biocide exposures 

observed in the Study cannot be considered to be necessarily representative of what 

would be expected to take place in the ballast tank environment. 

Laboratory Toxicology Testing Protocol. The Study’s laboratory toxicity tests 

employed a wide range of organisms and life stages, which is appropriate for evaluation 

of a proposed biocide. However, while the range of organisms was large (ranging from 

bacteria to fish), the logic for the selection of the organisms was not provided. Also, 

selection of a different set of test organisms, representing the same range of sizes and 

taxonomic groups might have led to different conclusions about the sensitivity to the 

hypochlorite. Consequently, the toxicity testing employed in the Study only can be 

considered preliminary because of the limited number of organisms per treatment, the 

small number of replicates per treatment, and the range of responses in the definitive 

tests. 

Further, it was not possible to fully evaluate the protocols used for the toxicity testing 

because in many cases the protocols were not available and the protocols that were 

supplied were not the ones used (e.g., there are protocols for 10-day toxicity tests with 

Hyalella azteca and Chironomus tentans, but neither were used). In several cases, the 

protocols used were In House protocols and were not described as part of the Study. 

Even where specific protocols were cited (e.g., for Artemia salina cysts), the full citation 

was not provided and the protocols could not be located. The data sheets were the only 

source of information on how tests were performed. Unfortunately, the problem was 

further complicated by the absence of some of the data sheets. 

In addition to the above, the presentation of the data and analyses was confusing. For 

example: (1) differences in water chemistry are identified in the Study, but the 

significance of these differences in the interpretation of results is not discussed; (2) LC99

numbers for saltwater tests referred to in the text of the Study do not match the 

numbers in the summary table for saltwater tests; and (3) test results for Eohaustorius

estuaries in laboratory and ballast saltwater are called “similar,” even though the ranges 

of the data are non-overlapping. 

The temperature selected for the studies was 15o

C. This temperature is not standard 

for many of the organisms studied and there should have been justification provided for 

the use of this temperature. The exposure duration selected for use with the Study was 

48 hours with no justification provided for its selection. However, the actual duration 

used varied in some instances based on the test organism (e.g., in the case of the 

Microtox test, the duration was only 15 minutes). For toxicity testing, a typical definitive 

test is conducted with five replicates with 5 - 20 organisms per replicate for each 

treatment. While the minimum number of test organisms per treatment is given as 20 
8 

(ASTM, 1998; USEPA, 1993), the usual number is generally more. The definitive tests 

did meet the standard criteria for minimum numbers of organisms per treatment, except 

for the tests with Daphnia neonates where n = 12; however, in many treatments, the 

range of response was either zero or 100 percent. Consequently, the ability to provide 

reliable estimates of the LC99 is limited. 

The analysis of the toxicity testing data was not conducted in a manner that permits any 

evaluation of the uncertainty of the response. In most cases, the data were analyzed by 

a linear interpolation and not by a more standard approach, such as use of logit or 

probit analysis. As a result, the 95 percent confidence limits for the LC99 have been 

minimized. For instance in Test 4121 (Bacillus subtilis spore), the data were analyzed 

with both the probit and linear extrapolation methods and it is clear that the more 

standard probit method leads to substantially larger confidence limits. The need to use 

the linear interpolation stems from the limited partial mortality data in many of the data 

sets. Often the result is either zero or 100 percent response. Further, in some cases 

(e.g., for Lubricous variegates, Test 4031), the control mortality was sufficient that it 

would invalidate the test. The method of addressing control mortality was not provided 

in the Study, which invalidates the results of that test. 

Finally, as with the shipboard tests, there was no quality control information provided on 

the health of the organisms used in laboratory toxicity tests. There should have been 

reference toxicity tests performed to ensure that the organisms used in the Study were 

of adequate health. 

Impact of Sediment. The shipboard and laboratory toxicity tests did not fully 

investigate the influence of sediments on the response to hypochlorite. There were 

range-finding tests performed in the presence of sediment, but the Study indicates that 

there were significant technical difficulties such that definitive tests could not be 

performed. Reasons for and information about the difficulties were not provided. The 

problems that were encountered in the laboratory have implications in the application of 

hypochlorite to systems where there are bedded sediments. Since it is clear from the 

Study that the amount and character of the sediments in the vessel will affect the 

amount of hypochlorite that must be used, obtaining definitive testing in the presence of 

sediment and developing a method to address the hypochlorite demand of sediments is 

crucial to proper application of hypochlorite as a ballast water disinfectant. The lack of 

any pertinent information on this factor further compromises the conclusions of the 

Study. 

Another consideration not addressed in the Study is the potential release of metals from 

ballast tank sediments as the result of the use of sodium hypochlorite. Treating soil and 

sediment samples with an oxidizing solution such as sodium hypochlorite or hydrogen 

peroxide is a common method of removing metals bound to the organic fraction of the 

soil or sediment (e.g., Laforce and Fendorf, 2000; Basta and Gradwohl, 2000; Usero et 

al., 1998). It is possible that during the treatment of ballast water containing sediments 

with sodium hypochlorite, metals could be released from the sediments. The amount of 

metal released would depend on the contact time of the sediment with the sodium 
9 

hypochlorite, the amount of metal associated with the sediment, the amount of 

sediment, and the fate of the metal when released to solution (e.g., does it reabsorb to 

the sediment). 

Biocide Discharge into the Great Lakes. Chlorine is widely used to disinfect drinking 

water and effluents from sewage treatment facilities. Hypochlorite solutions (e.g., 

sodium hypochlorite) are typically used and are very effective for chlorination. However, 

when chlorination is used to disinfect wastewater, residual chlorine that is discharged to 

surface waters can be toxic to aquatic life. Additionally, chlorination can form various 

chlorination by-products in water (i.e., disinfection by-products), depending on the 

amounts and type of organic matter that is present. At high levels, by-products formed 

by the chlorination of drinking water have been shown to cause cancer and 

developmental and reproductive problems in laboratory animals (e.g., trihalomethanes, 

haloacetic acids, and bromate) (USEPA, 2002). Ocean-going vessels take on ballast in 

various locations where the waters can have different constituent profiles. The varying 

characteristics of ballast water will likely affect the types and amounts of chlorinated 

compounds that are formed. 

Dechlorination reduces the toxic effects of chlorinated wastewater and reduces the 

formation of chlorination by-products. The use of sulfur salts (e.g., sulfur bisulfite) is a 

typical method for dechlorination. However, dechlorination to near zero amounts can be 

difficult. Additionally, over-dechlorination can lead to the formation of sulfates, reduced 

dissolved oxygen, and reduced pH in the effluent (USEPA, 2000).

The effectiveness of sodium bisulfite at neutralizing chlorine was evaluated in the Study 

through total residual chlorine measurements of ballast water test solutions before and 

after chlorination/dechlorination. In addition, a laboratory simulation test was conducted 

to assess potential formation of organic chemicals and related ballast water discharge 

acceptability to the state of Wisconsin. The results indicated that when sodium bisulfite 

was properly added and mixed with chlorinated ballast water, all theoretical total 

residual chlorine requirements (rather than actual since regulatory standards do not 

exist) for the state of Wisconsin could be met. No other Great Lakes jurisdictions were 

similarly evaluated. Also, the Study suggested that the levels of organic by-products 

formed through dechlorination would not exceed Michigan Water Quality Standards for 

a “typical, short-term intermittent discharge.” In both instances, insufficient information 

(too few tests and lack of data as to what the standards would be for the various other 

Great Lakes jurisdictions) was provided in the Study to definitively address the 

questions regarding the safety and legality of discharging chlorinated and/or 

dechlorinated ballast water into Great Lakes waters. Additional information and actual 

testing will be needed before this question can be addressed. 

The environmental effects of a full-scale implementation of a standardized chlorine 

ballast water treatment protocol of all Great Lakes transversing ocean-going ships were 

not addressed in the biocides Study. Small concentrations of the biocides within the 

ballast tanks of numerous ships could add up quickly when ballast tanks from multiple 
10 

ships are discharged into local harbors. This question should be evaluated in future 

studies. 

Laboratory Corrosion Testing Protocol. The Study’s choice of 3.5 percent sodium 

chloride as the test media for the corrosion tests was not reasonable since seawater is 

a medium with multiple living organisms that can affect corrosion rate, either by their 

physical presence (shielding), their metabolism (use and creation of corrosive 

compounds at the metal surface), and death (products of decay). A more realistic 

choice would have been to use fresh, natural seawater. 

Fifteen days was too short a time period to conduct the corrosion tests performed in the 

Study. Although water will permeate most coatings within this time period, anions like 

chloride will take much longer. Incubation times for coating degradation of epoxies can 

be over one year. For bare steel alone, the types of corrosion products that accumulate 

on the surface determine corrosion rate, and these products take much longer than 15 

days to come to an equilibrium configuration. Any corrosion data generated in 15 days 

on bare steel will be difficult to extrapolate to exposure times associated with ship 

service, while no corrosion effects are likely to show up on properly coated steel in this 

time frame. Any conclusions resulting from an investigation as short as that provided 

for in the Study cannot be considered definitive. 

In addition to the above, the Study’s lack of application of basic statistics in its analysis 

of some sections and its flawed use of statistics in other sections were problematic. For 

example, the Study’s conclusions regarding the significance of corrosion rates are not 

supported with any statistical analyses. It is unlikely that, if an analysis of variance had 

been performed on the data, there would have been any statistically significant effects 

of any of the variables except at the 95 percent confidence level. Similarly, the Study’s 

conclusions regarding creepage (coating deterioration) also are not supportable, since a 

15-day test is too short to overcome incubation time for coating deterioration in some 

cases. Again, if an analysis of variance was done on these data, it is unlikely that the 

results would show that any variable caused statistically significant change in creepage. 

Finally, a large environmental effect of discharging ballast water containing copper was 

not addressed in the Study. Extremely small amounts of copper, on the order of 20 

parts per billion (ppb), can cause catastrophic corrosion of aluminum by a process 

called heavy metal ion corrosion. This involves plating out of the copper on the 

aluminum to form micro-galvanic cells. This effect occurs in both fresh and salt water 

and can result in pitting depth growth rates on aluminum on the order of an inch per 

year (Hack, 2002) While the impact of such action would not be noticed by the large 

commercial ships, it would be by every owner of an aluminum-hulled boat that would be 

damaged. This issue would need to be investigated further in the event that future 

studies consider copper ion as a possible biocide for consideration. 
11 

Conclusions 

The following presents the MESB’s conclusions regarding efficacy of the two biocides 

evaluated, their ability to be discharged into waters of the Great Lakes, and their 

corrosion impact on ballast water tanks. 

Copper Ion Biocide Efficacy and Discharge Concentrations. Copper as an ion 

(e.g., Cu2+) is a naturally occurring chemical in the environment and necessary for 

various metabolic processes. For example, copper acts as a catalyst in the formation of 

hemoglobin, the iron-containing respiratory pigment in red blood cells (Sandstead, 

1995). At high concentrations, copper is toxic and is used to control algae and bacteria 

in swimming pools and lakes. The amount of copper to control algae depends on the 

other types of life forms in the water body. For example, if fish are present, then lower 

amounts of copper ion are used. 

Because of its toxic effects on biota such as fish, copper discharge to surface water is of 

concern. If a copper biocide treatment is used for ballast discharge, then this discharge 

water would most likely need to be regulated. The Study’s test results demonstrated 

that the copper ion biocide was only 33 percent effective at 167 ppb in freshwater and 

70 percent effective at 68 ppb in reducing bacteria in freshwater and simulated 

seawater experiments, respectively. These results suggest that at the concentrations 

tested, copper treatment was not effective. In order to be effective, even higher 

concentrations of copper would be needed, which would result in the further 

exceedance of the range of the theoretical allowable discharge concentration levels (2 

ppb to 48 ppb) determined by the Study for the Great Lakes jurisdictions. 

In addition to potential limits on copper concentrations that could be used, the efficacy 

of copper in killing biota ballast water is influenced by the natural geochemical behavior 

of copper in the environment. For example, copper is a particle reactive chemical. This 

means that it will tend to be adsorbed to sediments, whether suspended or settled. 

Consequently, the presence of sediment in the ballast tank would reduce the efficacy of 

copper as a biocide and higher concentrations of copper would need to be used 

compared to water in the absence of the sediment. 

The behavior and toxic effects of copper in water also are altered by natural processes, 

such as the formation of ion pairs in solution. In solution solutes, copper (Cu2+) can 

bond with other solutes, such as bicarbonate (HCO3

-

), to form new dissolve chemical 

species known as an ion pair or complex. In the example given, the ion pair would be 

copper bicarbonate (CuHCO3

-

). The formation of this ion pair decreases the toxicity of a 

copper (Stumm and Morgan, 1996). Since copper in solution is particularly influenced 

by the presence of dissolved organic matter, bicarbonate, and carbonate in water, 

changes in the relative abundances in these solutes might necessitate different 

amounts of copper concentrations needed as a biocide. This point is important to 

consider when interpreting the results of the Study’s simulated seawater experiments 

since, if the simulated solution did not contain proper amounts of solutes, such as 
12 

sulfate and bicarbonate, the experimental results observed in the Study might not 

represent the true behavior of copper. 

Copper ion concentrations in water of 0.02 to 0.05 ppm can cause severe corrosion of 

aluminum. For this reason, discharge of copper ion treated water from ballast tanks 

could cause significant corrosion of nearby aluminum-hulled boats and aluminum 

structures. It would be important to evaluate this issue further prior to proceeding with 

any additional consideration of copper ion as a ballast water biocide. 

In summary, the Study’s toxicity tests, as a whole, suggest that in sufficient 

concentrations, copper ion could be an effective biocide. However, at the 

concentrations needed to achieve the desired effectiveness, the level would be far too 

high to be discharged into the Great Lakes. Given this, and in the absence of any 

known neutralizing agent that would allow copper to be safely discharged into the Great 

Lakes, the MESB Panel concludes that copper ion cannot be considered to be a viable 

ballast water biocide alternative at this time. 

Sodium Hypochlorite Biocide Efficacy and Discharge Concentrations. The Study’s 

conclusions regarding the effectiveness of sodium hypochlorite as a viable ballast water 

biocide alternative from the shipboard and laboratory toxicity tests are limited and can 

only be considered preliminary at best. However, despite the problems outlined in this 

critique regarding the testing protocols used, the MESB Panel suggests that the use of 

sodium hypochlorite as a ballast water biocide can have a high degree of efficacy when 

treating the majority of organisms that were tested in the Study, assuming sufficient 

active hypochlorite concentration can be attained to account for sediment loads from 

both suspended and deposited material. Considerable more work will need to be 

conducted before any definitive statement regarding its efficacy within an actual ballast 

water tank environment can be made. In particular, well planned and controlled toxicity 

tests need to be conducted that will evaluate the biocide’s effectiveness on both benthic 

and resting stages of ANS in the presence of both suspended and bottom sediment 

similar to that found in ballast water tanks. Also, a mechanism needs to be developed 

and a careful analysis needs to be conducted that will determine how much chlorine 

remains available over time in the ballast tank in order to: (1) ensure the presence of an 

effective concentration of the biocide at the time when it is needed, and (2) allow for a 

determination to be made as to how much neutralizing compound would be needed for 

dechlorination prior to ballast water discharge. 

According to the Study, there exists no state or federal permitting requirements 

specifically for ballast water discharges and ballast water discharges are exempted from 

point-source discharge regulations. However, discharges of ballast water treated with 

sodium hypochlorite still would need to be of such quality so as to protect the 

designated uses of receiving waters. While the Study did attempt to address the issue 

of discharge of treated ballast water, the MESB Panel concludes that insufficient 

information (too few tests and lack of data as to what requirements would need to be 

met throughout the Great Lakes jurisdictions), was provided to definitively address the 

question regarding if such discharges could be safely and legally discharged into Great 
13 

Lakes waters. Additional studies involving the use of actual ballast water treated with 

the biocide and a clear indication as to what would be required by the various U.S. and 

Canadian Great Lakes jurisdictions in order to meet Great Lakes water quality 

standards would be useful. 

Finally, as seen in this Study and other investigations (e.g., Lubomudrov, Moll and 

Parsons, 1997) involving the use of only biocides to address ANS, the MESB Panel also 

concludes that biocide treatment in the absence of some other mechanism to address 

ballast water sediment, such as filtration, will result in an incomplete elimination of ANS. 

Future studies will need to address this problem by investigating the efficacy and the 

practicality of shipboard use of combined treatment methodologies. 

Impact of Biocides on Ballast Tank Corrosion. The biocide corrosion tests that were 

conducted in the Study were of too short a duration to allow prediction of long-term 

corrosion rates or coating degradation rates. Corrosion is not always constant over 

time, and, unless the time-dependence of corrosion rate is known, it is not possible to 

extrapolate data from short-term tests to predict long-term performance. In particular, 

coating degradation typically has an incubation time when the corrosive constituents are 

diffusing through the coating to the base metal underneath. For ballast water tank 

coatings, this incubation time can be many months. In addition, the tests should have 

used natural seawater and should have included cathodic protection for some of the 

exposures to better simulate the actual ballast water tank environment. 

The hypochlorous acid that is proposed as a biocide is an oxidant and could increase 

the corrosion of steel in water if present in quantities similar to the other oxidant in 

seawater, dissolved oxygen. The effect may become noticeable at concentrations of 1 

ppm or more if the kinetics of the reactions is favorable. Just as important, this oxidant 

may negatively affect the performance of paint systems on steel. Therefore, a new 

corrosion test should be conducted to determine the magnitude of these effects. 

Copper ion concentrations in water of 0.02 to 0.05 ppm can cause severe corrosion of 

aluminum. For this reason, discharge of copper ions from treated ballast tanks may 

cause significant corrosion of nearby aluminum-hulled boats and aluminum structures. 

It would be important to evaluate this issue further prior to proceeding with any 

additional consideration of copper ion as a ballast water biocide. 

Based on the information presented in the Study, the MESB is unable to reach definitive 

conclusions regarding the nature and extent of detrimental corrosion effects of either 

biocide on ballast tank structural integrity. Additional, better designed and longer 

duration tests will be needed to more fully evaluate this concern. 

15 

References Cited (1)

Allan, J.C. and A.S. Flecker. 1993. Biodiversity conservation in running water: identifying the major 

factors that threaten destruction of riverine species and ecosystems. Bioscience, 43:32-43. 

MESB-BW 9/24/2002 (2)

ASTM. 1998. Section 11, Water and Environmental Technology. IN Standard Guide for Conducting 

Acute Toxicity Test on Test Materials with Fishes, Macroinvertebrates, and Amphibians. E729-

96, Annual Book of ASTM Standards, Volume 11.05 Biological Effects and Environmental Fate; 

Biotechnology; Pesticides, American Society for Testing and Materials, West Conshohocken, 

Pennsylvania. MESB-BW 9/24/2002

Basta, N. and R. Gradwohl. 2000. Estimation of Cd, Pb, and Zn bioavailability in smelter-contaminated 

soils by a sequential extraction procedure. Journal of Soil Contamination, 9:149-164. MESB-BW 

9/24/2002

BMT Fleet Technology, Ltd. and ESG International, Inc. [2002]. [Draft] Final Report: Ballast Water 

Treatment Evaluation Using Copper and Sodium Hypochlorite as Ballast Water Biocides, April 12, 

2002. Kanata, Ontario. 730p. MESB-BW 4/23/2002

Coffey, B.T. and C.D. McNabb. 1974. Eurasian water-milfoil in Michigan. The Michigan Botanist, 

13:159-165. MESB-SS 5/27/1999

Designers & Planners, Inc and Herbert Engineering Corp. 1998. An Investigation into the Impacts of 

Performing a Ballast Water Exchange at Sea on Typical PANAMAX Containerships, November 9, 

1998. Report prepared for the U.S. Coast Guard, Washington, DC. MESB-BW 8/26/2002

Engler, J. [2002]. Correspondence to Dr. Lawrence Fischer, Michigan Environmental Science Board, 

April 10, 2002. Office of the Governor, Lansing. 2p. MESB-BW 4/23/2002

Hack, H. [2002]. Personal Communication to Keith G. Harrison, Michigan Environmental Science Board. 

Northrop Grumman Corporation, Oceanic Systems, Annapolis, Maryland. MESB-BW 9/24/2002

Harrison, K.G. (ed). 2002. MESB Ballast Water Biocides Investigation Panel Meeting Summary, May 28, 

2002. Michigan Environmental Science Board, Lansing. 29p. MESB-BW 5/28/2002

Keast, A. 1984. The introduced aquatic macrophyte, Myriophyllum spicatum, as habitat for fish and their 

invertebrate prey. Canadian Journal of Zoology, 62:1289-1303. MESB-SS 1/13/1999

Laforce, M.J. and S. Fendorf. 2000. Solid-phase iron characterization during common selective 

sequential extractions. Journal of the Soil Science Society of America, 64: 1608-1615. MESBBW 9/24/2002

Landrum, P.F. [2002]. Personal Communication to Keith G. Harrison, Michigan Environmental Science 

Board. Great Lakes Environmental Research Laboratory, U.S. Department of Commerce, Ann 

Arbor, Michigan. MESB-BW 9/24/2002

Laughton, R., T. Moran and G. Brown. 1992. A Review and Evaluation of Ballast Water Management 

and Treatment Options to Reduce the Potential for the Introduction of Non-native Species to the 

Great Lakes. Pollutech Technical Papers, No 22 (http://www.pollutech.com/papers/p22.htm). 

Pollutech Environmental Consultants, Oakville, Ontario, Canada. MESB-BW 8/26/2002 

______________ 

1. References with a bracketed date are unpublished and available through the Michigan Environmental Science Board. 

2. Michigan Environmental Science Board Document Reference Number. 
16 

Lloyd’s Register Engineering Services. 1995. Disinfection of Ballast Water: A Review of Potential 

Options , December 1995. Technical Investigation, Propulsion and Environmental Engineering 

Department, Lloyd’s Register Engineering Services. London, England. MESB-BW 8/26/2002

Locke, A., D.M. Reid, H.C. van Leeuwen, W.G. Sprules and J.T. Carlton. 1993. Ballast water exchange 

as a means of controlling dispersal of freshwater organisms by ships. Canadian J. Fish. Aquatic. 

Sci., 50:2086-2093. MESB-BW 9/24/2002

Lubomudrov, L.M., R.A. Moll and M.G. Parsons. [1997]. An Evaluation of the Feasibility and Efficacy of 

Biocide Application in Controlling the Release of Nonindigenous Aquatic Species from Ballast 

Water, November 1997. Report prepared for the Office of the Great Lakes, Michigan Department 

of Environmental Quality, Lansing. MESB-BW 8/26/2002

MacIsaac, H.J. 1996. Potential abiotic and biotic impacts of zebra mussels on inland waters of North 

America. American Zool., 36:287-299. MESB-BW 9/24/2002

Mack, R.N., D. Simberloff, W.M. Lonsdale, H. Evans, M. Clout and F.A. Bazzaz. 2000. Biotic invasions: 

causes, epidemiology, global consequences and control. Ecological Applications, 10:689-710. 

MESB-BW 8/26/2002

Mattice, J.S., and H.E. Zittel. 1976. Site-specific evaluation of power plant chlorination. 

J.W.P.C.F.,48:2284-2308. MESB-BW 9/24/2002

Mills, E.L., J.H. Leach, J.T. Carlton, and C.L. Secor. 1993. Exotic species in the Great Lakes: a history of 

biotic crises and anthropogenic introductions. Journal Great Lakes Research, 19:1-54. MESBBW 9/24/2002

NANPCA. 1990. Nonindigenous Aquatic Nuisance Prevention and Control Act of 1990. 16 USC 1990 

Title 16. MESB-BW 9/24/2002

Oemcke. D. 1999. The Treatment of Ships’ Ballast Water. Ecoports Monograph, Series No. 18, Ports 

Corporation of Queensland, Brisbane, Australia. MESB-BW 8/26/2002

Parsons, M.G. and R.W. Harkins. 2000. The Great Lakes ballast technology demonstration project 

filtration mechanical test program. Marine Technology, 37: 129-140. MESB-BW 8/26/2002

Ricciardi, A. 2001. Facilitative interactions among aquatic invaders: is an “invasional meltdown” 

occurring in the Great Lakes? Canadian Journal Fish. Aquatic Sci., 58:2513-2525. MESB-BW 

8/26/2002

Ricciardi, A. and H.J. MacIsaac. 2000. Recent mass invasion of the North American Great Lakes by 

Ponto-Caspian species. Trends Ecol. Evol., 15:62-65. MESB-BW 8/26/2002

Ricciardi, A., R.J. Neves, and J.B. Rasmussen. 1998. Impending extinctions of North American 

freshwater mussels (Unionoida) following the zebra mussel (Dreissena polymorpha) invasion. 

Journal of Animal Ecology, 67:613-619. MESB-BW 9/24/2002

Ryle. M. 1995. Ballast exchange needs utmost care. MOT Ship, 75:30-32. MESB-BW 9/24/2002

Sandstead, H.H. 1995. Requirements and toxicity of essential trace elements, illustrated by zinc and 

copper. American Journal of Clinical Nutrition, 61: 621S-624S. MESB-BW 9/24/2002

Stumm, W. and J.J. Morgan. 1996. Aquatic Chemistry. Wiley-Interscience, New York, New York. 

MESB-BW 8/26/2002
17 

USEPA. 2002. Disinfection Byproduct Health Effects, June 18, 2002. (http://www.epa.gov/enviro/html/ 

icr/dbp_health.html), U.S. Environmental Protection Agency, Washington, DC. MESB-BW 

8/26/2002

USEPA. 2000. Wastewater Technology Fact Sheet: Dechlorination, September 2000. EPA 832-F-00-

022, U.S. Environmental Protection Agency, Washington, DC. MESB-BW 9/24/2002

USEPA. 1993. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to 

Freshwater and Marine Organisms, August 1993. EPA 600/R-90/027F, U.S. Environmental 

Protection Agency, Washington, DC. MESB-BW 9/24/2002

Usero J., M. Gamero, J. Morillo and I. Gracia. 1998. Comparative study of three sequential extraction 

procedures for metals in marine sediments. Environment International, 24:487-496. MESB-BW 

9/24/2002 

19 

Appendix 1 

Executive Summary 

[Draft] Final Report: Ballast Water Treatment Evaluation 

Using Copper and Sodium Hypochlorite as Ballast Water Biocides

BMT Fleet Technology, Ltd. and ESG International, Inc. [2002]. [Draft] Final Report: Ballast Water Treatment 

Evaluation Using Copper and Sodium Hypochlorite as Ballast Water Biocides, April 12, 2002. Kanata, 

Ontario. 730p. 

21 

5264C.DFR 

Ballast Water Treatment Evaluation Using 

Copper and Sodium Hypochlorite 

as Ballast Water Biocides 

[Draft] FINAL REPORT 

12 April, 2002 

Submitted to: 

State of Michigan 

Department of Environmental Quality 

Surface Water Quality Division 

Constitution Hall 

525 West Allegan Street 

Lansing, Michigan 48913 

Submitted by 

BMT Fleet Technology Ltd. 

311 Legget Drive 

Kanata, Ontario 

K2K 1Z8 

In partnership with 

ESG International Inc. 

361 Southgate Drive 

Guelph, Ontario 

N1G 3M5 

Contact: David T Stocks 

Tel: 613-592-2830, Ext 223 

Fax: 613-592-4950 

E-mail: dstocks@fleetech.com 

23 

EXECUTIVE SUMMARY 

Numerous mechanical, physical, and chemical treatments, that may reduce aquatic nuisance species 

(ANS) introductions through the ballast water vector, are presently being investigated. This study was 

initiated to help the State of Michigan to determine if hypochlorite and copper can be recommended for 

general application as ballast water biocides. 

The biocidal properties of sodium hypochlorite and copper as they relate to ballast water treatment were 

evaluated in shipboard trials aboard the MV Federal Yukon, and in laboratory toxicity tests. Additionally, 

the potential detrimental effects of routine application of the biocides in ballast tanks were explored using 

accelerated corrosion experiments in the laboratory. Shipboard trials, conducted during a typical saltwater 

and freshwater voyage, indicate that sodium hypochlorite (dosed to a residual of ~10 ppm) significantly 

reduced (>90%) ambient zooplankton and bacteria levels relative to the controls after a two-hour 

treatment. In freshwater trials, copper ion treatment (< 0.2 ppm) was capable of reducing ambient 

zooplankton levels greater than 30% relative to the control. For both biocides, applied at these levels, 

numerous organisms were capable of surviving treatment in settled sediments. 

Laboratory toxicity tests were conducted on freshwater and saltwater fish, invertebrates, algae, and 

bacteria, in test conditions that simulate those in a ballast tank. Sodium hypochlorite was effective (i.e., 

achieved LC99) at killing the majority of species tested at less than Total Residual Chlorine (TRC) 10 

ppm. Higher sodium hypochlorite levels were required to kill encysted life stages. The LC99 and EC99 

values of the majority of species tested were at total copper levels below 200 ppm. The encysted life 

stages of certain test organisms were not killed at higher total copper levels. Exploratory range-finding 

tests suggest that the presence of high levels of sediment will negatively impact the performance of both 

biocides. 

Accelerated corrosion tests were conducted on bare, coated, and scribed metal coupons under a variety 

of conditions (i.e., fully submerged, periodic immersion, damp spaces, and buried in simulated sediment) 

in saltwater and freshwater. Test data suggests samples exposed to sodium hypochlorite tend to 

experience slightly more corrosion and paint damage than the control samples, however the effect is 

small and is not quantifiable in terms of life expectancy from this analysis. No accelerated failures were 

observed in any unscribed coating system due to the presence of sodium hypochlorite. Accelerated 

corrosion tests in solutions containing copper suggest in the aggressive corrosion environment of salt 

water and periodic immersion there is a slight increase in corrosion but there were no increases in coating 

failures observed. 

Numerous operational issues and constraints were identified during the conduct of the study. These 

include; 

• The removal of bottom sediment from ballast tanks and suspended sediment in incoming 

ballast water would likely have additional treatment benefits for both biocides. 

• Appropriate dosing and monitoring and distribution equipment will be required to ensure 

accurate biocide levels have been reached. 

• There are un-addressed safety issues surrounding the use of hypochlorite on ships, and 

classification societies and regulatory bodies would require special consideration of any onboard facility. 

• There are environmental discharge concerns associated with using copper. 

• The ranges of water qualities, particularly amount of sediment that can be expected to require 

treatment have yet to be identified. 

• Sodium hypochlorite is readily available throughout the Great Lakes ports or can be generated 

on board. 
24 

• Copper ion generators are capable of supplying copper ions to the ballast water intake. 

Economic models of typical on-board installations required to apply sodium hypochlorite or copper directly 

at the ballast water intake were investigated. It was shown that the life cycle cost of an onboard sodium 

hypochlorite generator and application system would increase the required charter rate necessary to 

maintain a return on the ship by $207 per day or 2.3% of a typical daily charter rate. To use manufactured 

sodium hypochlorite of a high concentration would cost $125 per day but increase the safety concern of 

handling on-board. The life cycle cost of a copper ion generator similar to that installed on the Federal 

Yukon using the same operational parameters would be $48 per day or an increase in charter rate of 

0.5%. 

The issue of sediment load and the detrimental effects it can have on the efficacy of biocides needs to be 

addressed: it should be quantified from both a tank bottom and intake water sediment perspective. 

Furthermore, it is possible that treatment of ballast water using biocides at every ballast operation may 

create a cumulative effect and tend to inactivate sediment borne biota. 
25 

Appendix 2 

April 10, 2002 Correspondence to the Michigan Environmental Science Board 

from Governor John Engler 

Engler, J. [2002]. Correspondence to Dr. Lawrence Fischer, Michigan Environmental Science Board, April 10, 2002. 

Office of the Governor, Lansing. 2p. 

27 
28 


AVAILABLE REPORTS (1993 - 2002) 

________________________________________________________________________ Gracki, J.A., R.A. Everett, H. Hack, P.F. Landrum, D.T. Long, B.J. Premo, S.C. Raaymakers, G.A. Stapleton and K.G. Harrison. 2002.

Critical Review of a Ballast Water Biocides Treatment Demonstration Project Using Copper and Sodium 

Hypochlorite, September 2002. Michigan Environmental Science Board, Lansing. xii + 30p. 

Premo, B.J., D.T. Long, R.J. Huggett, D. Premo, W.W. Taylor, G.T. Wolff and K.G. Harrison. 2001. Recommended Environmental 

Indicators Program for the State of Michigan, July 2001. Michigan Environmental Science Board, Lansing. x + 88p. 

Fischer, L.J., L Abriola, R.H. Kummler, D.T. Long, and K.G. Harrison. 2001. Evaluation of the Michigan Department of Environmental 

Quality’s Generic Groundwater and Soil Volitization to Indoor Air Inhalation Criteria, April 2001. Michigan Environmental 

Science Board, Lansing. x + 54p. 

Fischer, L.J., J.A. Gracki, D.T. Long, G.T. Wolff and K.G. Harrison. 2000. Health Effects of Low-Level Hydrogen Sulfide in Ambient 

Air, August 2000. Michigan Environmental Science Board, Lansing. x + 30p.

Gracki, J.A., M. DeVito, R.A. Etzel, M.A. Kamrin, W.B. Weil, G.T. Wolff and K.G. Harrison. 2000. Analysis of the Michigan Department of 

Environmental Quality’s Administered Environmental Standards to Protect Children’s Health, February 2000. Michigan 

Environmental Science Board, Lansing. x + 66p. 

Premo, B.J., T.R. Batterson, J.A. Gracki, C.D. McNabb and K.G. Harrison. 1999. Evaluation of the Use of Sonar® in Michigan, October 

1999. Michigan Environmental Science Board, Lansing. x + 97p. 

Fischer, L.J., R.Y. Demers, R.H. Kummler, G.M. Swanson and K.G. Harrison. 1999. Evaluation of the Risk of Cancer among Fire 

Fighters, June 1999. Michigan Environmental Science Board, Lansing, Michigan. 31p. 

Fischer, L.J., P.M. Bolger, J.L. Jacobson, B.J. Premo, E.O. van Ravenswaay and K.G. Harrison. 1998. Evaluation of Michigan’s 

Proposed 1998 Fish Advisory Program, January 1998. Michigan Environmental Science Board, Lansing. vi + 67p. 

Long, D.T., W.E. Cooper, W.B. Harrison III, R.H. Olsen, B.J. Premo and K.G. Harrison. 1997. Evaluation of Directional Drilling 

under the Great Lakes, October 1997. Michigan Environmental Science Board, Lansing. 8p. 

Fischer, L.J., R.Y. Demers, J. R. Harkema, R.H. Kummler, K.R. Rosenman, G.T. Wolff and K.G. Harrison. 1997. Evaluation of Air Quality 

and Human Health Issues involving Particulate Matter and Ozone, August 1997. Michigan Environmental Science Board, 

Lansing. xii + 82p. 

Fischer, L.J., P.M. Bolger, G.P. Carlson, J.L. Jacobson, M.A. Roberts, P.T. Thomas, K.B. Wallace and K.G. Harrison. 1997. (Impact of 

New PCB Information on 1995 MESB-Council of Great Lakes Governors Special Fish Advisory Report), Correspondence 

to Governor John Engler, January 21, 1997. Michigan Environmental Science Board, Lansing, Michigan. 10p. 

Premo, B.J., J.E. Carey, L.J. Fischer, D.T. Long, D.J. Morrissey, C.E. Nagle and K.G. Harrison. 1996. Evaluation of Michigan's LowLevel Radioactive Waste Isolation Facility Siting Criteria, June 1996. Michigan Environmental Science Board, Lansing. xiv + 

94p. 

Fischer, L.J., P.M. Bolger, G.P. Carlson, J.L. Jacobson, B.A. Knuth, M.J. Radike, M.A. Roberts, P.T. Thomas, K.B. Wallace and K.G. 

Harrison. 1995. Critical Review of a Proposed Uniform Great Lakes Fish Advisory Protocol, September 1995. Michigan 

Environmental Science Board, Lansing. xii + 62p. 

Bulkley, J.W., R.Y. Demers, D.T. Long, G.T. Wolff and K.G. Harrison. 1995. The Impacts of Lead in Michigan, March 1995. Michigan 

Environmental Science Board, Lansing. xii + 48p. 

Olsen, R.H., B.J. Premo and K.G. Harrison. 1994. (Report on Bacteriological and Macrophyte Contamination of Lake St. Clair), 

Correspondence to Governor John Engler, August 26, 1994. Michigan Environmental Science Board, Lansing. 2p. 

Fischer, L.J., R.J. Cook, R.Y. Demers, B.J. Premo, E.O. van Ravenswaay and K.G. Harrison. 1994. Impacts of Chlorine Use on 

Environmental and Public Health, June 1994. Michigan Environmental Science Board, Lansing. x + 67p. 

Fischer, L.J., J.W. Bulkley, R.J. Cook, R.Y. Demers, D.T. Long, R.H. Olsen, B.J. Premo, E.O. van Ravenswaay, G.T. Wolff and K.G. 

Harrison. 1993. Mercury in Michigan's Environment: Environmental and Human Health Concerns, April 1993. Michigan 

Environmental Science Board, Lansing. xii + 144p. 

______________________________________________________________________________________________________________ 

Copies of the above reports may be obtained free of charge by either writing to:

Michigan Environmental Science Board 

Constitution Hall, 5th Floor, P.O. Box 30680, Lansing, Michigan 48909-8180 

or downloading from the MESB Internet Home Page at <http:/www.michigan.gov/mesb>