Tributyltin (TBT) Flashcards

1
Q

What is Biofouling?

A

Settlement and accumulation of living organisms on man-made physical structures placed in an aquatic or marine environment

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2
Q

What fouling organisms are there?

A
bacterial slime
diatoms
algae
sponges
tubeworms
bryozoa
mussels
barnacles
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3
Q

Why is biofouling economically important?

A
  • increases frictional resistance (drag) in fouled ships
  • structural deterioration (corrosion) of engineered materials
  • restricted flow through fouled aquaculture cage netting
  • mechanical blockage of intake and outfall pipes
  • losses in heat transfer efficiency of marine cooling systems
  • increased costs for maintaining/replacing all of the above
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4
Q

What effects does biofouling have on speed and fuel consumption?

A
  • Can reduce vessel speed by up to 10%
  • 10 micrometer increase in average hull roughness can result in 0.3 to 1% increase in fuel consumption
  • up to 40% increase in fuel consumption needed to counter drag
  • large vessels fuel costs can be as much as 50 percent of operating costs
  • US navy spends ~1 billion dollars on extra fuel and maintenance to counter effects of biofouling
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5
Q

Why are antifoulants beneficial?

A

Saves shipping industry 7.2 millions tonnes of fuel per annum
Estimates saving of 22 million tonnes of CO2

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6
Q

How do antifouling paints work?

A
  • Work by releasing small amounts of biocides at paint surface, killing settling stages of fouling organisms
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7
Q

Points about TBT

A
  • introduced in the 1960s and proved very effective
  • degrades through debutylisation (triBT, diBT, monoBT)
  • biodegradable
    • action of bacteria and phytoplankton aids the breakdown
    • higher temperature and nitrate supplementation promote breakdown
    • adsoprtion on particles leads to incorporation into sediments
    • half life ~2 years reported for anaerobic sediments
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8
Q

Stats regarding TBT in Rotterdam harbour

A
  • 20 million tonnes of sludge dredged annually
  • TBT in sediments 500 times acceptable levels
  • 16 million tonnes dumped at sea
  • 4 million tonnes considered “heavily contaminated”
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9
Q

What is the danger of TBT?

A
  • caused a decline in oysters and whelks in 1960s in UK and France
  • Investigations in Plymouth in 1960s showed high degree of imposex (masuclinisation) in dog whelps
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10
Q

Dog Whelk stats

A

Dog whelk (Nucella lapillus)

  • widely distributed on rocky shores from Straits of Gibraltar to Arctic
  • Gonochoristic (one of 2 distinct sexes)
  • lays vase shaped egg capsules attached to rocky substrate
  • direct development (no planktonic stage)
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11
Q

How many species of gastropod have been found to be affected with imposex?

A

72 spp. (Schulte-Oehlmann et al., 1997)

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12
Q

What is the toxicity of TBT to other organisms?

A
  • Molluscs - most sensitive (<10ng/l)
  • Copepods, echinoderms, polychaetes, tunicates 10-100ng/l range
  • Fish (adult), decapod crustacea relatively resistant
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13
Q

How can otters and bottlenose dolphins be linked to TBT?

A

bioaccumulation - dead otters and stranded dolphins can have extremely high levels of TBT in their livers
TBT is known to cause immunosurpression leaving them vulnerable to infections

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14
Q

What and when were the regulations imposed on TBT?

A
  • French reugulate use of TBT (1983)
  • British ban use on boats under 25m (1985)
  • US congress pass regulations (1988)
  • IMO resolution (1990)
  • draft proposal to phase out TBT by 2006 (1996)
  • TBT banned on ships (2007)
  • EC782/2003 bans applications on EU flagged vessels and as of 2008 becomes an offence for any ship visiting an EU port to have TBT present on its hull
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15
Q

What happened after the bans?

A
  • TBT breaks down in 1-3 months in aerobic conditions
  • bivalve recruitment dramatically improved
  • imposex reduced, but still observed 7 years after French ban
  • Deposit feeding bivalves showed no recovery 2 years after ban
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16
Q

How is recovery monitored?

A

Skipjack tuna being used as a biomonitor

- show high levels up to 400ng/g around Japan and developing Asian countries

17
Q

What must an optimal antifouling coat be and not be?

A
Must be 
- anticorrosive
- antifouling
- environmentally acceptable
- long life
- compatible with underlying system
- resistant to abrasion/biodegradation/erosion
- capable of protection regardless of whether boat is moving or not
- smooth
Must not be 
- toxic to environment
- persistent in the environment
- expensive
- chemically unstable
- a target for non-specific species
18
Q

What are the other antifouling options?

A
  • toxic chemicals
  • natural biocides
  • repellants (physical and chemical)
19
Q

Name and describe some non TBT biocidal paints

A
  • heavy metals and booster biocides
    e. g. igarol 1051, triacine herbicide used with copper preparations
  • UK igarol restricted to vessels >25m
  • Diuron banned in UK
  • Medetomidine
  • MEXEL 432
20
Q

Disadvantages of non TBT paints

A
  • Toxic to aquatic organisms

- 2-3x more expensive than TBT paints

21
Q

Points about MEXEL 432

A
  • Toxic effects have been reported
  • Osmoregulatory disruption and decreased gill Na+/K+ATPase activity observed in flatfish
  • oxidative stress responses seen in gills of other fish
  • emulsion covered by world wide patents made from alkyl amines
  • active emulsion having dispersant properties
  • controls colonisation and proliferation of micro and macro organisms at surface, including mussel colonisation
22
Q

What types of natural biocides are there?

A
  • bacteria
  • porifera (sponges)
  • algae
  • cnidaria (corals)
  • echinoderms
  • tunicates
  • tannins from hard wood trees
23
Q

What are the characteristics of natural chemical antifouling agents and give example?

A
  • Often secondary metabolites
  • Classified according to metabolic pathway
  • Biomimetics at molecular level
  • Performance tested initially using barnacle settlement bioassay
  • e.g. halogenated furanone from red seaweed Delisea pulchra best so far EC50 0.02 micrograms/ml-1
24
Q

What are foul release coatings?

A

E.g silicone elastomeric coatings
- non-toxic
- designed to mimic low surface energy of animals like whales and dolphins
- broad spectrum
Disadvantages
- do not resist fouling when vessel is docked, vessel needs to reach speed to lose fouling
- increases ability to translocate alien species

25
Q

What other method of anti-fouling is there with regards to sharks?

A

Shark skin ships - shark scales topped with even smaller spines or bristles

  • combination plastic and rubber coating replicates a version of shark skin made up of billions of tiny raised, diamond-shaped patterns
  • each sharklet diamond measures 15 microns and contains seven raised ribs that resemble different lengths of raised horizontal bars
  • irregular surface makes it difficult for plant spores to get a good grip
26
Q

What is ultrasonic antifouling?

A
  • low frequency sound waves create a wall of moving water molecules over submerged hull
  • microenvironment deters attachment of algae and barnacles
27
Q

Additional reading Biofouling - costs

A

Schultz et al., 2010
Costs more to clean and paint ships than they cost in fuel (~56 million per year)
Adams et al., 2011
Costs shellfish culturing industry ~15% of annual operation costs

28
Q

Additional reading TBT - goldfish

A

Zhang et al., 2016
Can induce obesogen response in goldfish (Carassius auratus)
- increased food and weight gain

29
Q

Additional reading TBT - traira

A

Feraro et al., 2004
Showed that TBT had mutagenic effects on fish nucleus
Study on traira (Hopius malabaricus)

30
Q

Additional reading TBT - gastropods

A

Schulte-Oehlmann et al., 1996

Hydrobia ulvae increased levels of imposex and reproductive failure

31
Q

Additional reading TBT - terrestrial

A

Silva et al., 2013
Earthworms very sensitive - increased mortality rate
Isopods showed an avoidance response to soils contaminated with TBT
Some seeds failed to germinate

32
Q

Additional reading future methods - microbes

A

Dobretsov et al., 2005
Showed microbes could be used to prevent biofouling - marine bacteria and diatoms
- inhibit microorganisms + settlement of invert larvae + microalgal species

33
Q

Additional reading future methods - insects

A

Gangadoo et al., 2016
Used insect cuticles as templates
- cicadas and dragonfly wings