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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
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