FLEETTECHNOLOGY LTD

Copper Ion and Hypochlorite

as Ballast Water Biocides

M.E.S.B. Lansing

May 29 2002

FLEETTECHNOLOGY LTD

Project ObjectivesMichigan’s Ballast Water Work Group • Are they effective in killing a broad

range of ballast-borne biota?• Can they be safely handled?• Are the ultimate discharge

concentrations environmentally acceptable to regulatory agencies?

• Do they damage ballast tanks?• Do they work with sediment

present?• Are they economical and readily

available?• Are there any other practical

considerations regarding their use?

• Management practices and biocides are the only two methods currently available to deal with this problem.

• Hypochlorite and copper ion are potentially currently available ballast water biocides.

• On-board field testing of these two biocides should be carried out as soon as possible.

Slide 1

FLEETTECHNOLOGY LTD

Project ComponentsShip board

Field trial on board M.V. Federal Yukon

Toxicity Lab

Toxicity testing in simulated / controlled

conditions

Corrosion Lab

Tank Coatings and corrosion testing in

simulated / controlled conditions.

Slide 2

FLEETTECHNOLOGY LTD

Ship Board TrialBallast Cycle Marine Ports Europe

Ballast Cycle Fresh Water Ports Great Lakes

NOBOB Voyage

Chlorine residual verified as compliant, test liquid discharged

Ballast tanks filled to establish permissible discharge dilution levels

Hypochlorite tested by manual dosing using Decant tanks and test barrels

Copper Ion tested by Biomatic Ion generator dosing ballast tanks and extracting to test barrels

Actual NOBOB Tank residuals collected to provide sediment loads

Biota concentrated to develop meaningful data

Live Dead Data collected Biocide levels monitored

Slide 3

FLEETTECHNOLOGY LTD

Toxicity laboratory testingHypochlorite and Copper ion

• Testing conducted in freshwater and saltwater• Test conditions altered simulate ballast tank conditions (dark, cool) during a short voyage (48 hours)

• Tests conducted on fish, invertebrates (benthic and pelagic, resting stages) algae, and bacteria

Slide 4

FLEETTECHNOLOGY LTD

Corrosion Laboratory testingCoatings Condition Environment Biocide Medium

Bare Metal

Coated intact

Fresh Water

4 Systems Zinc Pre-

weld primer

Epoxy & modified Epoxy

Coated & Scribed

Humid (suspended above

water surface)

Submerged constantly

Splash zone (mounted on wheel)

Buried

(in inert sand)

2 Hypochlorite

levels

2 Copper levels

(separate)

Controls

Salt Water

Slide 5

FLEETTECHNOLOGY LTD

Results - Ship board

BacteriaZooplankton

-100.0

-80.0-60.0

-40.0

-20.00.0

20.0

40.0

60.080.0

100.0

1

Freshw ater Saltw ater

DB D B

Hypochlorite

BacteriaZooplankton

-100.00

-80.00

-60.00-40.00

-20.00

0.00

20.00

40.0060.00

80.00

100.00

1

Freshw ater Saltw aterCopper ion

-126%

Slide 6

FLEETTECHNOLOGY LTD

Results - Toxicity LabHypochlorite toxicity to selected organisms in the laboratory (48 hr LC99)

Lethal Concentration Range (ppm) Freshwater Marine

< 1 Alga S. capricornutum Bacteria V. fischeri Alga Nanochloris sp. Alga S. costatum

Alga S. obliquus Invertebrate D. magna (neonate)

1 to 10 Bacteria Bacillus subtilis Amphipod E. estuarius

Mollusc D. polymorpha Fish C. variegatus Benthic invertebrate L. variegates

Fish C. carpio

10 to 100 Invertebrate D. magna – (ephippia)

100 to 1000 Invertebrate A.salina (cyst)

Slide 7

FLEETTECHNOLOGY LTD

Results - Toxicity LabCopper ion toxicity to selected organisms in the laboratory (48 hr LC99)

Lethal Concentration Range (mg/L) Freshwater Marine < 0.2 Invertebrate D. magna (neonate) Alga S. capricornutum Alga Nanochloris sp. 0.2 to 2.0 Alga S. obliquus Bacteria V. fischeri Fish C. carpio 2.0 to 20 Mollusc D. polymorpha Alga S. costatum Benthic invertebrate L. variegatus 20 – 200 Invertebrate D. magna - ephippia Amphipod E. estuarius Fish (C. variegates) > 1000 Bacteria Bacillus subtilis Invertebrate A.salina (cyst)

Slide 8

FLEETTECHNOLOGY LTD

Results - Corrosion Hypochlorite

-3.5

-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

Anu

aliz

ed T

hick

ness

cha

nge

(mm

/yea

r)

SALT WATER

CONTROL LOW CHLORINE

HIGH CHLORINE

FRESH WATER

CONTROL LOW CHLORINE

HIGH CHLORINE

Wheel periodic immersion

Submerged constantly wet

Humid In the damp space

Burried in sediment

Slide 9

FLEETTECHNOLOGY LTD

Results - Coating HypochloriteASTM score - versus - location in tank

(Average across Control and Chlorine levels)

7

7.5

8

8.5

9

9.5

10

Wheel Submerged Humid Buried

CoatingSample 1

CoatingSample 2

CoatingSample 4

Average

ASTM Score - versus - Chlorine level (average across all coatings)

7

7.5

8

8.5

9

9.5

10

Control FW Low Chlorine FW High Chlorine Control SW Low Chlorine SW High Chlorine

Wheel

Submerged

Humid

Buried

Average

Slide 10

FLEETTECHNOLOGY LTD

Results - Copper

ASTM score - versus - location in tank (Average across control and copper levels)

7.5

8

8.5

9

9.5

10

Wheel Submerged Humid Buried

Coating Sample 1

Coating Sample 2

Coating Sample 3

Coating Sample 4

Average

-3.5

-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

Ann

ualiz

ed T

hick

ness

cha

nge

(mm

/yea

r)

SALT WATER

CONTROL LOW COPPER

HIGH COPPER

FRESH WATER

CONTROL LOW COPPER

HIGH COPPER

Wheel periodic immersion

Submerged constantly wet

Humid In the damp

Burried in sediment

Slide 11

FLEETTECHNOLOGY LTD

Structural members form collection areas for bottom sediment

Transverse wash bulkhead with drainage hole

Bottom sediment settled in dead area

Overlying water in bilge radius area

Ship tanksDecant tanks

on Deck

Section through cargo hold

Upper wing tank

Inner bottom tank

Connecting pipe

Access

Main Deck

Ship bottom

Access to bottom tank

Slide 12

FLEETTECHNOLOGY LTD

Fitting Copper Generator

Slide 13

FLEETTECHNOLOGY LTD

Impact on Shipping

0.67%1.16%2.31%0.53%%increase to cost of shipping

$ 60.54$104.03$ 207.73$ 48.08 Increase charter to maintain return

15151520 Amortization period

3%3%3%3%Inflation rate

15%15%15%15%Return rate

$9,000$9,000$9,000$9,000 Vessel charter rate (per day)

$ 756$ 504$318$ 0.09 Raw material costs

12121212Ballast operations per year

555 5Element replacement frequency (years)

$10,000$ 10,000$ 50,000$18,750 Element replacement cost

$ 77,318$ 207,025$ 437,710$104,696 Capital cost

Deliver to the ship as required

Buy and store onboard

330 kg (725lbs) per day 0.8%

0.2 ppm on 50 tonnes

Item

Purchase commercial concentration Sodium

Hypochlorite

On Board Chlorine

Generation

Copper Ion Generator

Slide 14

FLEETTECHNOLOGY LTD

Summary of Findings - EfficacyShip board studies demonstrated that in both fresh and sea water;

Lab studies demonstrated that in both fresh and sea water;

Hypochlorite is very effective (>90%) in reducing bacteria levels and killing many zooplankton taken in with ballast water at concentrations of ~10 mg/l (as TRC).

A copper ion generator dosing at 0.2 mg/l is of limited effectiveness in killing organisms taken in with water ballast (33% of zooplankton were killed, and bacteria were essentially unaffected).

Hypochlorite is very effective (>99%) in killing most organism types at a concentration of 10 mg/l.

Exceptions are resting stages such as eggs and cysts, which required much higher doses of hypochlorite for comparable kill

Copper is very effective (>99%) in killing most organism types at a concentration of 20 mg/l (as total copper).

Higher doses of copper ion were not effective at killing resting stages such as eggs and cysts.

Both hypochlorite and copper ion are hindered in their biocidal action by sediments in ballast water.

It is critical to minimize sediment in ballast water ( Best ManaIt is critical to minimize sediment in ballast water ( Best Management Practices)gement Practices)..

Slide 15

FLEETTECHNOLOGY LTD

Summary of Findings - OperationalCopper ion biocide can

be safely handled,

is relatively low cost, and

requires no special training or safety precautions on-board ship.

Copper Ion generation on board is always available.

There are no quantifiable, detrimental effects of copper on the structural integrity of the ship.

Copper discharge rates are unlikely to meet environmental regulatory standards if applied at effective dosages.

Hypochlorite can be safely handled, provided that;

proper accommodations and procedures are in place for both the hypochlorite and the neutralizing agent (sodium bisulfite).

Depending on the concentration / volume stored and or carried, this includes;

Storage tanks, piping, pumps, metering, monitoring and control, crew training, safety procedures.

Bulk hypochlorite is readily available at ports or may be generated on board from common salt.

Over a typical life time exposure to hypochlorite at a concentration of 10 mg/l TRC, ballast tank coating degradation and corrosion is not significantly increased. Corrosion becomes more significant at higher levels of hypochlorite.

Hypochlorite discharge levels can be achieved by addition of neutralizing agent. By products are acceptable to regulators.

Slide 16

FLEETTECHNOLOGY LTD

Way AheadIn order to answer questions about the efficacy and practicality of hypochlorite and copper ion with sediment and plankton present, further testing should be done in actual ballast tanks and various harbor water quality situations.

The total dosage necessary to achieve an effective kill increases for both biocides in ballast water containing high amounts of sediment and the minimum level is indeterminate. Studies are needed to determine the magnitude of this effect due to both suspended sediment entering with ballast water, and settled sediment in the ballast tanks.

Costs, efficacy, regulatory acceptability, and practicality can all be affected by sediments

Sediment can minimized through Best Management Practices, this needs to be quantified.

Slide 17