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A new antifouling principle based on no-release coatings. Hans Elwing, Professor Ph.D.

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A new antifouling principle based on no-release coatings Hans Elwing, Professor Ph.D. Dep. of Chemistry and Mol. Biol. University of Gothenburg Sweden The Barnacle - our target Algae, slime and other animals
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A new antifouling principle based on no-release coatings Hans Elwing, Professor Ph.D. Dep. of Chemistry and Mol. Biol. University of Gothenburg Sweden The Barnacle - our target Algae, slime and other animals are also important biofoulers but not as serious as barnacles. The Barnacle A crustacean, present in all marine environments Destroy coatings by penetration Typical fouling on a sailing boat in Sweden (one summer season) Green algae Dramatic increase in Drag! Copper paint Barnacle Also a safety and seaworthiness problem! Barnacles prefer small propellers Polished Propeller lfalck Barnacle covered Propeller Barnacle covered VOLVO Penta propeller 20 % propulsion reduction Leads to ton extra CO2 and extra 9 milj EURO fuel cost in Sweden Testbed investigation of the hydrodynamic properties of barnacle covered propeller (SSPA, Sweden) Macrocyclic lactones against barnacle colonisation Macrocyclic lactons (MCL) are producesd by Actinomyces - soil living bacteria. MCLs are used as pesticides, crop protection and anti-parasitic drugs. Two international anti-fouling projects: 1. Christine Kritikou (PI and CEO, ENTARCO SA) Greece. They use spinosad: 2. Hans Elwing (PI) Göteborg University, Sweden. We use Avermectins subform: Ivermectin MCL are highly toxic to most crustaceans, non-toxic to mammals and very inexpensive Field experiment Ivermectin additive - three months Trace amount Effect of Hard and Soft Binders Non-erosive paint formulations used here for research purpose only diffusion Soft (butyl-methacrylate) Hard (styrene) Time Time The idea was to slow down leaking rate, by eliminating release bydegradation Penetration effects of barnacle in soft and hard non-erosive coatings. No Avermectin added. Front Backside Soft (Butyl- Metha- Crylate) See paint at side! See penetration! Hard Styrene No paint at side No penetration! Photo: Mats Hulander Time resolved field settling Ivermectin 0.1 % side Control side Hard Coating (Styrene) Soft Coating (Butylmetha- Crylate) Small Barnacle No Barnacle No Barnacle Immersion time 14 days 55 days 80 days Release rates Release rate of Ivermectin (0.1%) in NON-EROSIVE coatings Ivermectin release rate, hard and soft no-erosive coatings - ISO standard ASTM rotating cylinder method with HPLC MS/MS analysis LC/MS-MS LOQ=0,03ng/cm2/day (Highest Release level in erosive coatings) ng/cm2/day 2,5 2 1,5 1 0,5 0 Ivermectin (0.1%) release rate from hard and soft experimental coatings 2,27 1,37 0,37 The release rate of Ivermectin is at least times lower than Cu and times lower than most biocides used in anti-fouling paints. The ISO method overestimate release rate by 3-5 times 0,18 0,26 0,08 0,07 0,10 0,00 0,00 0,04 0,00 0,04 0,00 0,00 0,04 0,07 0,00 0,00 0,00 0,00 0, Immersion time in the ISO-Aquarium expressed in Days Hard Soft Model of Biocide action Ivermectin Model of action on SOFT coatings Coating Without Ivermectin Small barnacle Support Soft baseplate Living tissue Coating Penetration Adult Barnacle Hard baseplate With Ivermectin Iv Iv Iv A Detachment A Iv Intoxication Wikstrom, SA; Pavia, H Chemical settlement inhibition versus post-settlement mortality as an explanation for differential fouling of two congeneric seaweeds OECOLOGIA Volume: 138 Issue: 2 Pages: Published: JAN 2004 Natural Phenomena! Ivermectin Model of action on HARD coatings Without Ivermectin Small barnacle Early hard baseplate Adult Barnacle No penetration Support With Ivermectin Adult Barnacle Small barnacle Early hard baseplate Iv Iv Iv Iv One molecular explanation to the low (no) leaking rates of avermectin (ivermectin) coatings. Affinity to the solid/water interface. Measured with a simple screening method Optical surface sensitive methods, ellipsometry, SPR Affinity Water Biocide Spincoated polymer(binder) surface Reflecting surface Adsorbed mass Injection (1ug/ml) of Biocide Rinse Adsorption No Adsorption Time Binding of some biocides to rosin layers in water environment Biocide Affinity to rosin/water Leaking rate (ug/cm 2 /day) Paint Concentration (%) This study (partly litterature) (litterature) Ivermectin Very High (or abscent) 0.1 Medetomidine Medium Econea Medium/Trace 1 1 Sea-Nine Low 1 1 Tolyfluanid Low 1 1 Spinosad Low n.d 1 Copper Low Biocide High Interfacial concentration of Biocide at the binder/water interface Coatings Low binder/water affinity High binder/water affinity Dahlstrom M, Jonsson PR, Lausmaa J, Arnebrant T, Sjogren, M, Holmberg, K Martensson, LGE, and Elwing, H BIOTECHNOLOGY AND BIOENGINEERING 86, 1, 1-8, 2004 Hans Elwing, Mia Dahlstöm, Mattias Berglin, Thomas Arnebrant, Liselott Lindh, Magnus Nyden, Lena Mårtensson, Per Johnsson. Swedish patent (2005) Boat experiments Control Surface Avermectin Surface Soft anti-fouling paint. Four month in Swedish coastal water. Photo and Boat owner: Jesper Eriksson 2008 Photo of propeller after cleaning. Outer propeller painted with Prop & Drev. Inner propeller coated with Prop & Drev containing 0.1 % Ivermectin. Lasse Bengtsson 2009 Control surface 3y Duration of Ivermectin containing coating. The hull was painted 2009 with Ivermectin (0.1%) containing paint formulations. The photograph above was taken in Oct days in sea water without repainting. Very few barnacles where present at the hull. Ecotoxicology The calculated toxicity risk of copper and Avermectins is about equal with regard to the concentration factor: 30% Copper, 0.1% ivermectin ( Corophium volutator) But The relative leaking rate of Ivermectin is very low compared with copper in erosive (rosin-based) paints. No leaking in non-erosive paints BUT FULL ANTI-BARNACLE EFFECT! The avermectins(ivermectin) are only toxic to the target organism, but copper is generally toxic to all (biofouling) organisms The avermectins are fully degradable and of biological origin The avermectins do not knowingly affect mammals copper does! Summary Ivermectin additive in trace amounts (0.1%) in soft coatings is a very efficient method of preventing barnacle colonisation for several seasons. No anticolonisation effect on hard coating despite release. The antifouling effect of ivermectin is related to the close contact of the newly metamorphosed/adult barnacle at the coating surface. The emission rates of Ivermectin to the marine environment is dependent on the coating and is (near) zero in our experimental coatings WITH A PRESERVED ANTI-BARNACLE EFFECT! In Swedish coastal water, ivermectin out-conquer copper performance in marine antifouling paint formulations according to small boat owners. A new surface sensitive selection method of biocide-binder systems have been developed (discovered). Its use may lead to development of paint formulations with very low release rates of biocides. Reference Pinori, E ; Berglin, M Brive, LM ; Hulander, M Dahlstrom, M Elwing, H Multi-seasonal barnacle (Balanus improvisus) protection achieved by trace amounts of a macrocyclic lactone (ivermectin) included in rosinbased coatings BIOFOULING, 27, 9, DOI: / Published: 2011 Next step To further develop a binder system, with no release of Avermectin (Ivermectin) To develop co-biocide systems also active against algae, slime and other invertebrate target organisms Combination with physical methods Vision No copper or other heavy metals in marine antifouling coatings Only biocides of natural origin will be used and the emission rates of biocides will be very low Handling and destruction of old coatings will be developed Acknowledgements: The group Emiliano Pinori PhD student soon released GU/SP Dr Mattias Berglin Ass Prof GU/SP Dr Mia Dahlström GU/SP Mats Hulander PhD student GU Dr Lena Brive M.Sc LC/MS/MS SP Dr Jukka Lausmaa Scientific director SP Simon the mascot and grandson Marin Biofouling - Some figures 20-40% increased fuel consumption. Fuel costs associated with fouling amount to about 10 billion $. Biofouling problems are present in aquaculture, (salmon), seawaterbased heat exchangers, desalinisation plants and nuclear power plants. Total world market estimates to 1-2 billion /Year From: Townsin, R.L. (2003) The ship hull fouling penalty. Biofouling 19 (supplement), Degradable paint formulations (Commonly used) Controlled release of biocides in classic toxic paints leakage Biocide in coating Biocide dissolved in water Thickness or weight Time
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