### 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 Environmen tal Science Board

Ballast Water Biocides Investigation Panel

MICHIGAN ENVIRONMEN TAL SCIENCE BOARD CONSTITUTION HALL, 5TH FLOOR SOUTH

525 WEST ALLEGAN STREET

P.O. BOX 30680 LANSING, MICHIGAN 48909-8180

SEPTEMBER 2002MICHIGAN 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. Raaym akers, B.S.C. ..... (International Maritime Organization) ................. Panel Member Gregory A. Staple ton 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. Fisch er, Ph.D. .........................................................................................Chair Raymond Y. De mers, 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. Prem o, 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 Environm ental 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 Environm ental Science Board

Ballast Water Biocides Investigation Panel

MICHIGAN ENVIRONMEN TAL 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 Unit ed 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 Bi ocides Treatment Demonstration Project Using Copper and Sodium Hypochlorite , September 2002. Michigan Environmental Science Board, Lansing. xii + 30p.iii TABLE OF CONTENTS Page

Major Findings a nd Conclusions ................................................................................................. ........... vii

Introduc tion ................................................................................................................... .............................. 1

Charge to the Michigan Envi ronmental Scie nce Boar d.......................................................................... 2

Overview of the Biocides Study ................................................................................................. ............... 3 Shipboard Toxi city Tests...................................................................................................... ............... 3 Laboratory Toxi city T ests..................................................................................................... ............... 3 Laboratory Co rrosion Tests .................................................................................................... ............ 4 Summary of St udy Conc lusions .................................................................................................. ....... 4

Michigan Environmental Science Boar d Crit ique.................................................................................. .. 5 Shipboard Toxicology Testing Protocol ......................................................................................... ... 5 Laboratory Toxicology Testing Protocol ........................................................................................ ... 7 Impact of Sediment ............................................................................................................ .................. 8 Biocide Discharge in to the Grea t Lakes. ....................................................................................... .... 9 Laboratory Corrosion Testing Protocol. ........................................................................................ .. 10

Conclusions.................................................................................................................... ........................... 11 Copper Ion Biocide Efficacy and Discharge C oncentrat ions......................................................... 11 Sodium Hypochlorite Biocide Effica cy and Discharge Concentrat ions....................................... 12 Impact of Biocides on Ba llast 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 Gover nor John E ngler................................................................................ 25v 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 Michiganvii Critical Review of a Ballast Water Bi ocide 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 t hese, 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 S t. Lawrence Seaway in 1959. Seventy percent of the

ANS discovered since 1985 in the Great Lakes are nat ive to fresh and brackish waters of the PontoCaspian region (Black, Caspian and Azov Seas) in Eu rasia. The introduction of ANS has played a major role in modifying aquatic ecosystems within the Grea t Lakes Basin. The primary route of ANS entry into the Great Lakes has been through ballast water exc hange 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 bioci des, 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 subcontractor s, 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 Sc ience Board (MESB) review the final draft Study and evaluate the scientific validity of the conclusions r eached 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., Cu 2+ ) 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 p ools 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 mo st likely need to be regulated. The Study’s test results demonstrated that the copper ion biocide wa s 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 conc entrations tested, copper

treatment was not effective. In order to be effect ive, 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 geoc hemical 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 conc entrations of copper would need to be used compared

to water in the absence of the sediment. Th is 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 (Cu 2+ ) can bond with other solutes, such as bicarbonate (HCO 3 - ), 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 di ssolved organic matter, bicarbonate, and carbonate in water, changes in the relative abundances in these solutes might ne cessitate different amounts of copper concentrationsviii needed as a biocide. This point is important to co nsider when interpreting the results of the Study’s simulated seawater experiments si nce, if the simulated solution did not contain proper amounts of solutes, such as sulfate and bicarbonate, the ex perimental results observed in the Study might not represent the true behavior of copper.

Copper ion concentrations in water of 0.02 to 0.05 pp m 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 al uminum 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 dat a, as a whole, suggest that in su fficiently 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 di scharged into the Great Lakes. Given this, and in the absence of any known neutralizing agent that woul d allow copper to be safely discharged into the Great Lakes, the MESB Panel conclu des that copper ion cannot be co nsidered to be a viable ballast

water biocide alternative at this time.

♦ Sodium Hypochlorite Biocide. The Study’s conclusions regardi ng the effectiveness of sodium hypochlorite as a viable ballast water biocide alternat ive 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 test ing protocols used, the MESB Panel suggests that the use of sodium hypochlorite as a ballast water biocide can have a hi gh 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 e fficacy within an actual ballast water tank environment can be made. In part icular, well planned and controlled toxicity tests need

to be conducted that will evaluate the biocide’s e ffectiveness on both benthic and resting stages of ANS in the presence of both suspended and bottom sediment similar to that found in ba llast 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 ba llast tank in order to: (1) ensure the presence of

an effective concentration of the bioc ide 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 balla st water discharges are exempted from point-source discharge regulations. However, di scharges of ballast water treated wi th sodium hypochlorite still would need to be of such quality so as to protect the desi gnated uses of receiving waters. While the Study did attempt to address the issue of discharge of treat ed ballast water, the MESB Panel concludes that insufficient information (too few tests and lack of da ta 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 discha rged 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 investi gating the efficacy and the practicality of shipboard use of combined treatment methodologies.

♦ Biocide Corrosivity. The biocide corrosion tests that were c onducted in the Study were of too short a duration to allow prediction of long-term corrosion ra tes or coating degradation rates. Corrosion is not always constant over time, and, unless the time-dependen ce of corrosion rate is known, it is not possibleix to extrapolate data from short-term tests to predic t 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 wate r tank coatings, this incubation time can be many months. In addition, the tests should have used na tural seawater and should have included cathodic protection for some of the exposures to better si mulate 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 kinet ics of the reactions is favorable. Just as important, this oxidant may neg atively affect the perform ance 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, t he 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 dura tion tests will be needed to more fully evaluate this

concern.

### Critical Review of a

Ballast Water Biocide Tre atment Demonstration Project

Using Copper and Sodium Hypochlorite

(A Science Report to Governor John Engler)1 Introduction

Over 160 nonindigenous aquatic nuisance spec ies (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 num ber of the introductions coin ciding with t he 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, su ch 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 factor s that regulate the ANS populations in their nativ e 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, m any of the ANS have severely disrupted Great Lakes native plant and anim al species populations a nd ecosystem functions (Mack et

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

The primary route of ANS ent ry 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 ca rries 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 ar e released into the system every year. Pursuant to the federal N onindigenous Aquatic Nuisance Prevention and Control Act of 1990, as am ended (NANPCA, 1990), some sh ips 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 t hat 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 Engi neering 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 balla st on board (NOBOB) are exempt from the regulations. NOBOB ships c an still contain substantial amounts of unpumpable water

and sediment in their balla st tanks and, therefore, harbor adult organisms, dinonflagellate cysts, and diatom resting spor es. Consequently, other control methods such as filtration, heat, ultraviolet light, and a variety of different types of biocides

treatments also are be ing studied in an effort to find an effective method or combination2 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 internati onal and domestic shi pping industries, and

the U.S. Coast Guard to examine potential ballast water treatments including technologies, management prac tices, and biocides. The Ballast Water Working Group (BWWG) focused on what was currently ava ilable 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 availabl e methods for dealing with the problem were management practices and bioci des. The BWWG defined a currently available method as: (1) not needing extensive research to estab lish the efficacy of the biocide, (2) not needing extensive ship retrofitting, and (3) no t 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 t he biocides should be carried out as soon as possible. In February 2001, the BWWG reco mmended that a third bi ocide, copper ion, be added to the list of potentia l biocides. In May 2001, t he MDEQ issued a request for proposals for shipboard biocid e 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 subcont ractor was ESG International of Guelph, Ontario. The final draft report of the demonstr ation project (Study), entitled Ballast Water Treatment Evaluation Using Copper and Sodium Hypoc hlorite as Ballast Water Biocides (BMT Fleet Technology, Ltd. and ESG Internati onal, Inc. 2002, see Appendix 1), was completed in April 2002.

Charge to the Michigan Environmental Science Board

On April 10, 2002, Governor Engler (E ngler, 2002) requested t hat the Michigan Environmental Science Board (MESB) review the final draft Study and evaluate the scientific validity of the conc lusions reached regarding the:

1. Efficacy of the two biocides evaluated;

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

3. Discharge concentrations for eac h biocide needed to meet regulatory standards (see Appendix 2).

On April 14, 2002, a Ballast Wa ter 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 in dependent review of the Study by the Panel3 members and a meeting (May 29, 2002) of the Panel, at which test imony and Study’s supportive documentation were presented and discussed (Harrison, 2002).

Overview of th e 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 dem onstration 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 op erations of the ship. The Study was not allowed to interfere with the commercial oper ations of the ship and certain on-site modifications to the experi mental plan were necessary to accommodate the local biological conditions and eng ineering difficulties encountered. The tests were

conducted on the deck of the sh ip using 55-gallon plastic bar rels as test chambers. Additionally, a deck-mounted decant tank (a metal tank typically reserved for capturing cargo wash water prior to discharge) was m odified and coated with paint used in the ballast tanks for additional hypochlorite tests.

A typical voyage profile for a ship on internat ional trade into the Great Lakes consists of loading cargo overseas and transiting the oc ean 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 disch arge that ballast and take on an out-bound cargo. The shipboard dem onstration 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 por t): Cargo was taken on and ballast water discharged, creati ng a NOBOB condition.

• Great Lakes Port #1 (Great Lakes fr eshwater port): Ca rgo was off-loaded

and ballast water taken on.

• Great Lakes Port #2 (Great Lakes fr eshwater 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 bioc ides as it relates to the treatment of organisms in ballast water. The toxicity testing was conducted on freshwater and saltwater fish, invertebrates, alg ae, and bacteria. In addition, the toxicity of the biocides to selected ANS resting stages was evaluated. In certain in stances, 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 wi thout the presence of clean control sediment for characterizing the effect of sediment on biocide efficacy.4 Laboratory Corrosion Tests. The purpose of the labor atory corrosion testing portion of the Study was to examine the possible detr imental 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 coat ing systems and base metals typically used in the construction of ships ballast tanks were in vestigated in a specially adapted corrosion tank. The different conditions of metal expo sure 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” experi ment to show the effects on structure covered with sediment. The experiment us ed 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 fres hwater voyage indicate that sodium hypochlorite (dosed to a residual of approximately 10 parts per million - ppm) significantly reduced (>90%) ambient zooplankt on and bacteria levels relative to the

controls after a two-hour tr eatment. In freshwater tria ls, copper ion treatment (<0.2 ppm) was capable of reducing ambient zoopl ankton levels greater than 30 percent

relative to the control. For both biocides applied at these leve ls, numerous organisms were capable of surviving treatment in settled sediments.

Laboratory biocide toxicity tests condu cted on freshwater and saltwater fish, invertebrates, algae, and bacteria , in test conditions that simu late those in a ballast tank showed that sodium hypochlorite was effective (i.e., achieved LC 99 – the lethal

concentration of substance that results in 99% mortality in a population) with the majority of species tested at less than a to tal residual chlorine of 10 ppm. Higher sodium hypochlorite levels were requir ed to kill encysted life stages. The LC 99 and EC 99 (the effective concentration of a substanc e that results in 99% growth reduction, hatchability, or mortality in a po pulation) values of the majority of species tested were at total copper levels below 200 ppm. The en cysted life stages of cert ain 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) co rrosion tests conducted on bar e, coated, and scribed metal coupons under a variety of cond itions (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 sa mples; 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 s light increase in corrosion, but there were no increases in coating failures.5 Michigan Environmental Science Board Critique

The following MESB critique addresses conc erns regarding the general experimental protocols used and conclusions reached in the Study. The critique focuses on sodium hypochlorite, although most of the methodological and inte rpretation concerns also apply to copper ion.

Shipboard Toxicology Testing Protocol. In general, the MESB Panel found that the shipboard experimental des ign was not clear and was fu rther complicated by the following issues:

1. The distribution of treatments am ong 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. Th is 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 fille d through fire mains, thus bypassing ballast tanks, while others were filled from ballast tanks. This difference confounds the ability to ascribe differenc es solely to the presence of the biocide, or to compare among combi nations 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 evi dently 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 t he 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 experiment al design, many of the specifics for the methods used in the shipboard tests were mi ssing, including such critical items as

methods of collection and additi on of organisms to test c hambers, number of samples per container, procedures for handling samp les, 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 met hod 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 incl uded 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 cyst s and live benthic organisms found in the

sediment. Recent work at the Great Lakes Environmental Research Laboratory (Landrum, 2002) indicates that concentrati ons 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 addit ion, 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 orga nisms and the exposures were done with a sub-sample of the water of unknown volu me. It was not clea r 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. Addi tional detail in the protocols regarding this iss ue 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 rep licates 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 met hod for determining these values was not provided. Because of the absen ce of the supporting information, it is not possible to be certain about the validity of these values. There was an in dication in the Study that significant numbers of organisms could not be recovered at t he end of the trials. It was not clear, however, if this was just for t he treatments or also for the controls.

The temperature of the shi pboard tests varied from 12 to 20 degrees centigrade ( o C), but the laboratory tests were performed at 15 o C. The impact of the temperature on the toxicity testing was not evaluated. Cha nges 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 ship board test results directly, it does make the setting of a

toxicant dose from labor atory data problematic.7 Finally, the conditions that existed the St udy’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 w ould be needed for actual ballast tank

disinfection. Given the inabil ity of the Study to duplicate ba llast tank structure and the complications of mixing in an actual ballast tank envir onment, 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 organi sms and life stages, which is appropriate for evaluation of a proposed biocide. However, while t he range of organisms was large (ranging from bacteria to fish), the logic for the selecti on of the organisms was not provided. Also, selection of a different set of test organism s, representing the sa me range of sizes and taxonomic groups might have led to different conclusions about the sensitivity to the hypochlorite. Consequently, the toxicity te sting employed in the Study only can be considered preliminary becaus e 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 prot ocols were not available a nd 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 descr ibed 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 protoc ols could not be located. The data sheets were the only source of information on how tests were per formed. 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 an alyses was confusing. For example: (1) differences in water chemis try are identified in the Study, but the significance of these differences in the inte rpretation of results is not discussed; (2) LC 99 numbers for saltwater tests referred to in the text of the Study do not match the numbers in the summary table for saltwa ter 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 15 o C. This temperatur e is not standard for many of the organisms studied and there s hould have been justification provided for the use of this temperature. The exposure duration select ed for use with the Study was 48 hours with no justification pr ovided for its selection. Ho wever, 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 minimu m number of test organisms per treatment is given as 208 (ASTM, 1998; USEPA, 1993), the usual number is generally more. The definitive tests

did meet the standard criteria for minimum numbers of organi sms 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 LC 99 is limited.

The analysis of the toxicity testing data wa s not conducted in a manner that permits any evaluation of the uncertainty of the response. In most ca ses, the data were analyzed by a linear interpolation and not by a more st andard approach, such as use of logit or probit analysis. As a result, the 95 percent confidence limits for the LC 99 have been minimized. For instance in Test 4121 ( Bacillus subtilis spore), the data were analyzed with both the probit and linea r extrapolation methods and it is clear that the more standard probit method leads to substantially larger confidence limit s. The need to use the linear interpolation stems fr om the limited partial mortalit y 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 ad dressing control mortality was not provided in the Study, which invalidates the results of that test.

Finally, as with the shipboard te sts, there was no quality contro l information provided on the health of the organisms used in laboratory toxicity test s. 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 t he response to hypochlorite. There were range-finding tests performed in the presence of sediment, but the Study indicates that there were significant technical difficultie s 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 implic ations in the application of hypochlorite to systems where t here are bedded sediments. Si nce it is clear from the Study that the amount and char acter 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 fu rther compromises the conclusions of the Study.

Another consideration not addre ssed in the Study is the potent ial release of metals from

ballast tank sediments as the result of the us e of sodium hypochlorite. Treating soil and sediment samples with an oxidizing solution such as sodium hypoc hlorite or hydrogen peroxide is a common method of removing meta ls bound to the organic fraction of the soil or sediment (e.g., Laforce and Fe ndorf, 2000; Basta and Gradwohl, 2000; Usero et

al ., 1998). It is possible that during the treatm ent of ballast water containing sediments with sodium hypochlorite, metals could be re leased from the sedime nts. The amount of metal released would depend on the contact ti me of the sediment with the sodium9 hypochlorite, the amount of metal associ ated with the sediment, the amount of sediment, and the fate of the metal when releas ed 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 fa cilities. Hypochlorite solutions (e.g., sodium hypochlorite) are typically used and are very effective for chlo rination. However,

when chlorination is used to disinfect wastew ater, 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., di sinfection 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 di fferent constituent pr ofiles. 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 neut ralizing chlorine was evaluated in the Study through total residual chlorine measurements of ballast wa ter test solutions before and

after chlorination/dechlorination. In additi on, a laboratory simulation test was conducted to assess potential formation of organic chemic als and related balla st water discharge acceptability to the state of Wisconsin. The re sults indicated that when sodium bisulfite was properly added and mixed with chlorinated ballast water, all theoretical total residual chlorine requ irements (rather than actual since regulatory standards do not exist) for the state of Wiscons in could be met. No other Great Lakes jurisdictions were similarly evaluated. Also, the Study suggest ed that the levels of organic by-products formed through dechlorination would not e xceed 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 legalit y of discharging chlorinated and/or

dechlorinated ballast water into Great Lakes waters. Additi onal information and actual testing will be needed before this question can be addressed.

The environmental effects of a full-scale implementation of a st andardized chlorine ballast water treatment protocol of all Gr eat Lakes transversing ocean-going ships were

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

ballast tanks of numerous sh ips could add up quickly when bal last tanks from multiple10 ships are discharged into lo cal harbors. This question s hould 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 reasonabl e since seawater is a medium with multiple living or ganisms that can affect corr osion rate, either by their physical presence (shielding), their met abolism (use and creation of corrosive compounds at the metal surface), and death (p roducts 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 coat ings 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 corrosi on products that accumulate on the surface determine corrosion rate, and thes e 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 effect s 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 Stud y’s lack of application of bas ic statistics in its analysis

of some sections and its flawed use of statis tics in other sections were problematic. For example, the Study’s conclusi ons regarding the significanc e of corrosion rates are not supported with any statistical an alyses. 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 (c oating deterioration) also ar e not supportable, since a 15-day test is too short to overcome incuba tion 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 di scharging ballast water containing copper was not addressed in the Study. Ex tremely small amounts of c opper, 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 ow ner of an aluminum-hulled boat that would be damaged. This issue would need to be investi gated 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 a nd Discharge Concentrations. Copper as an ion (e.g., Cu 2+ ) is a naturally occurring chemical in the environment and necessary for various metabolic processes. For example, c opper acts as a catalyst in the formation of hemoglobin, the iron-containi ng respiratory pigment in red blood cells (Sandstead, 1995). At high concentrations, copper is toxic and is used to contro l 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 perc ent effective at 167 ppb in freshwater and 70 percent effective at 68 ppb in reduci ng 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 dischar ge concentration levels (2 ppb to 48 ppb) determined by the Study fo r the Great Lakes jurisdictions.

In addition to potential limits on copper concent rations 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, c opper is a particle reactive chemical. This

means that it will tend to be adsorbed to sediments, whet her suspended or settled. Consequently, the presence of sediment in the bal last tank would reduce the efficacy of copper as a biocide and higher concentra tions of copper woul d need to be used compared to water in the absence of the sediment.

The behavior and toxic effects of copper in water also are al tered by natural processes, such as the formation of ion pairs in so lution. In solution solutes, copper (Cu 2+ ) can bond with other solutes, su ch as bicarbonate (HCO 3 - ), to form new dissolve chemical species known as an ion pair or complex. In the exampl e given, the ion pair would be copper bicarbonate (CuHCO 3 - ). The formation of this ion pa ir decreases the toxicity of a copper (Stumm and Morgan, 1996). Since copper in solution is particularly influenced by the presence of dissolved organic matte r, bicarbonate, and carbonate in water, changes in the relative abundances in t hese solutes might necessitate different amounts of copper concentrations needed as a biocide. This point is important to consider when interpreting the results of t he Study’s simulated seawater experiments since, if the simulated solution did not co ntain proper amounts of solutes, such as12 sulfate and bicarbonate, the experimental results observ ed 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 near by aluminum-hulled boats and aluminum structures. It would be import ant to evaluate this issue furt her 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 e ffective 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 sa fely discharged into the Great Lakes, the MESB Panel concludes that copp er ion cannot be considered to be a viable

ballast water biocide alternative at this time.

Sodium Hypochlorite Biocide Effi cacy and Discharge Concentrations. The Study’s conclusions regarding the effect iveness 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 bioc ide can have a high degree of efficacy when treating the majority of organisms that we re tested in the Study, assuming sufficient active hypochlorite concentra tion can be attained to acc ount for sediment loads from both suspended and deposited ma terial. Considerable more work will need to be conducted before any defin itive statement regardi ng its efficacy within an actual ballast water tank environment can be made. In parti cular, well planned and controlled toxicity

tests need to be conduct ed that will evaluate the biocide’ s effectiveness on both benthic and resting stages of ANS in the presenc e of both suspended and bottom sediment

similar to that found in ballast water tan ks. 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 t ank 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 wate r discharges and ballast water di scharges are exempted from point-source discharge regulatio ns. 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, th e 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 disc harges could be safely and le gally discharged into Great13 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 or der to meet Great Lakes water quality

standards would be useful.

Finally, as seen in this Study and other in vestigations (e.g., Lubomudrov, Moll and Parsons, 1997) involving the use of only bioc ides 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 in complete elimination of ANS. Future studies will need to address this pr oblem by investigating the efficacy and the practicality of shipboard use of combined treatment methodologies.

Impact of Biocides on Ba llast Tank Corrosion. The biocide corrosion tests that were conducted in the Study were of too short a duration to allow pr ediction 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 per formance. In particular, coating degradation typically has an incubati on 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 incl uded 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 pai nt systems on steel. Therefore, a new

corrosion test should be conducted to determi ne 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 c opper ions from treated ballast tanks may cause significant corrosion of nearby alum inum-hulled boats and alum inum structures. It would be important to evaluate this i ssue further prior to proceeding with any additional consideration of copper i on 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 corrosi on effects of either

biocide on ballast tank stru ctural integrity. Addition al, 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, Oce anic Systems, Annapolis, Maryland. MESB-BW 9/24/2002

Harrison, K.G. (ed). 2002. MESB Ballast Water Biocides Inve stigation 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 Labo ratory, 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 fo r the Introduction of Non-native Species to the

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

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

______________ 1. References with a bracketed date are unpublished and ava ilable through the Michigan Envi ronmental 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 Engine ering 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 organi sms 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 F easibility and Efficacy of Biocide Application in Controlling the Release of Nonindigenous Aquatic Species from Ballast

Water , November 1997. Report prepared for the Of fice 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. Lonsda le, H. Evans, M. Clout and F.A. Ba zzaz. 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-spe cific 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 Pr evention 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 Gr eat 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 ma ss 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 8/26/200217 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 a nd I. Gracia. 1998. Comparative st udy of three sequential extraction procedures for metals in marine sediments. Environment International , 24:487-496. MESB-BW

9/24/200219 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: Ba llast 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.com23 EXECUTIVE SUMMARY

Numerous mechanical, physical, and chemical treat ments, 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 deter mine if hypochlorite and copper can be recommended for general application as ballast water biocides.

The biocidal properties of sodium hypochlorite and c opper 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 ro utine 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 hypochlo rite (dosed to a residual of ~10 ppm) significantly reduced (>90%) ambient zooplankton and bacteria le vels 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 c ontrol. For both biocides, applied at these levels, numerous organisms were capable of surv iving treatment in settled sediments.

Laboratory toxicity tests were conducted on freshw ater 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 te sted at less than Total Re sidual Chlorine (TRC) 10 ppm. Higher sodium hypochlorite levels were requ ired 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 pres ence of high levels of sediment will neg atively 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 immers ion, 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 expectan cy 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 sugges t 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 distri bution 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 w ould 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 th roughout the Great Lakes ports or can be generated

on board.24 • Copper ion generators are capable of supplyi ng copper ions to the ballast water intake.

Economic models of typical on-board installations requir ed to apply sodium hypochlorite or copper directly at the ballast water intake were investigated. It wa s 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 co st $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 effect s 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.2728AVAILABLE 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. 2 002.

Critical Review of a Ballast Water Biocides Treatme nt 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.

Fi scher, 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. Pr emo, E.O. van Ravenswaay and K.G. Harrison. 1998

. Evaluation of Michigan’s Proposed 1998 Fish Advisory Program, January 1998 . Michigan Environmental Scienc e 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 Sci ence 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>