Diatom community structure on commercially available ship hull coatings

Diatoms are primary colonizers of both antifouling and fouling-release ship hull coatings. There are few published studies which report on diatom community development on modern ship hull coatings. This study reports diatom communities on eight commercial marine ship hull coatings exposed at three static immersion sites along the east coast of Florida, viz. Daytona, Sebastian, and Miami. The coatings tested were three ablative copper systems (Ameron ABC-3, International BRA-640, and Hempel Olympic 76600), two copper-free biocidal systems (E-Paint SN-1, Sherwin Williams HMF), and three fouling-release (FR) systems (International Intersleek 700, International Intersleek 900, and Hempel Hempasil). One hundred and twenty-seven species comprising 44 genera were identified, including some of the more commonly known foulers, viz. Achnanthes, Amphora, Cocconeis, Entomoneis, Licmophora, Melosira, Navicula, Nitzschia, Synedra, and Toxarium. A significant difference was seen among sites, with the more estuarine site, Sebastian, having lower overall diatom abundance and higher diversity than Daytona and Miami. Copper coatings were primarily fouled by Amphora delicatissima and Entomoneis pseudoduplex. Copper-free coatings were fouled by Cyclophora tenuis, A. delicatissima, Achnanthes manifera, and Amphora bigibba. FR surfaces were typified by C. tenuis, and several species of Amphora. The presence of C. tenuis is new to the biofouling literature, but as new coatings are developed, this diatom may be one of many that prove to be problematic for static immersion. Results show coatings can be significantly influenced by geographical area, highlighting the need to test ship hull coatings in locations similar to where they will be utilized.     

Diatom community structure on in-service cruise ship hulls

Diatoms are an important component of marine biofilms found on ship hulls. However, there are only a few published studies that describe the presence and abundance of diatoms on ships, and none that relate to modern ship hull coatings. This study investigated the diatom community structure on two in-service cruise ships with the same cruise cycles, one coated with an antifouling (AF) system (copper self-polishing copolymer) and the other coated with a silicone fouling-release (FR) system. Biofilm samples were collected during dry docking from representative areas of the ship and these provided information on the horizontal and vertical zonation of the hull, and intact and damaged coating and niche areas. Diatoms from the genera Achnanthes, Amphora and Navicula were the most common, regardless of horizontal ship zonation and coating type. Other genera were abundant, but their presence was more dependent on the ship zonation and coating type. Samples collected from damaged areas of the hull coating had a similar community composition to undamaged areas, but with higher diatom abundance. Diatom fouling on the niche areas differed from that of the surrounding ship hull and paralleled previous studies that investigated differences in diatom community structure on static and dynamically exposed coatings; niche areas were similar to static immersion and the hull to dynamic immersion. Additionally, diatom richness was greater on the ship with the FR coating, including the identification of several new genera to the biofouling literature, viz. Lampriscus and Thalassiophysa. These results are the first to describe diatom community composition on in-service ship hulls coated with a FR system. This class of coatings appears to have a larger diatom community compared to copper-based AF systems, with new diatom genera that have the ability to stick to ship hulls and withstand hydrodynamic forces, thus creating the potential for new problematic species in the biofilm.     

Diatom community structure on commercially available ship hull coatings

Diatoms are primary colonizers of both antifouling and fouling-release ship hull coatings. There are few published studies which report on diatom community development on modern ship hull coatings. This study reports diatom communities on eight commercial marine ship hull coatings exposed at three static immersion sites along the east coast of Florida, viz. Daytona, Sebastian, and Miami. The coatings tested were three ablative copper systems (Ameron ABC-3, International BRA-640, and Hempel Olympic 76600), two copper-free biocidal systems (E-Paint SN-1, Sherwin Williams HMF), and three fouling-release (FR) systems (International Intersleek 700, International Intersleek 900, and Hempel Hempasil). One hundred and twenty-seven species comprising 44 genera were identified, including some of the more commonly known foulers, viz. Achnanthes, Amphora, Cocconeis, Entomoneis, Licmophora, Melosira, Navicula, Nitzschia, Synedra, and Toxarium. A significant difference was seen among sites, with the more estuarine site, Sebastian, having lower overall diatom abundance and higher diversity than Daytona and Miami. Copper coatings were primarily fouled by Amphora delicatissima and Entomoneis pseudoduplex. Copper-free coatings were fouled by Cyclophora tenuis, A. delicatissima, Achnanthes manifera, and Amphora bigibba. FR surfaces were typified by C. tenuis, and several species of Amphora. The presence of C. tenuis is new to the biofouling literature, but as new coatings are developed, this diatom may be one of many that prove to be problematic for static immersion. Results show coatings can be significantly influenced by geographical area, highlighting the need to test ship hull coatings in locations similar to where they will be utilized.     

Biological succession on silicone fouling‐release surfaces: Long‐term exposure tests in the harbour of ischia,Italy

A static test site was set up in the Harbour of Ischia (Gulf of Naples, Italy) to investigate the antifouling effectiveness of newly developed non‐polluting coatings. Two‐year exposure experiments were performed on sets of panels coated with silicone‐based coatings, and results were compared both to sets of panels coated with toxic agents, and non‐toxic epoxydic compounds. Abiotic factors, strength of adhesion of the temporal dynamics of succession of foulers were analyzed throughout the period of immersion. Brown algae constantly represented the “border point”; between the early community, dominated by sume, micro‐ and macroalgae, and the late community, mainly represented by bryozoans and molluscs, as well as polychaetes, sponges and tunicates. Brown algae, such as Ectocarpus siliculosus, tunicates (mainly Botryllus schlossen) and polychaetes (Hydroides elegans, Pileolaria pseudomilitaris) were demonstrated to be key species, triggering the community and influencing its development. Light was the main abiotic factor discriminating the community on the two sides of panels exposed to different irradiances. The best performing coatings (silicone easy release coatings without additives) substantially influenced community structure, shifting it to the earliest stages of colonization. Silicone coatings proved to be unsuitable for colonization by organisms typical of mature communities, due to their low energy surfaces. The results of the present paper demonstrate that silicone coatings technology represents an alternative to the use of biocidal antifouling paints.     

The development of marine biofilms on two commercial non-biocidal coatings: a comparison between silicone and fluoropolymer technologies

The antimicrobial performance of two fouling-release coating systems, Intersleek 700® (IS700; silicone technology), Intersleek 900® (IS900; fluoropolymer technology) and a tie coat (TC, control surface) was investigated in a short term (10 days) field experiment conducted at a depth of ca 0.5 m in the Marina Bandar Rawdha (Muscat, Oman). Microfouling on coated glass slides was analyzed using epifluorescence microscopy and adenosine-5′-triphosphate (ATP) luminometry. All the coatings developed biofilms composed of heterotrophic bacteria, cyanobacteria, seven species of diatoms (2 species of Navicula, Cylindrotheca sp., Nitzschia sp., Amphora sp., Diploneis sp., and Bacillaria sp.) and algal spores (Ulva sp.). IS900 had significantly thinner biofilms with fewer diatom species, no algal spores and the least number of bacteria in comparison with IS700 and the TC. The ATP readings did not correspond to the numbers of bacteria and diatoms in the biofilms. The density of diatoms was negatively correlated with the density of the bacteria in biofilms on the IS900 coating, and, conversely, diatom density was positively correlated in biofilms on the TC. The higher antifouling efficacy of IS900 over IS700 may lead to lower roughness and thus lower fuel consumption for those vessels that utilise the IS900 fouling-release coating.     

Amphiphilic hydrolyzable polydimethylsiloxane-b-poly(ethyleneglycol methacrylate-co-trialkylsilyl methacrylate) block copolymers for marine coatings. II. Antifouling laboratory tests and field trials

Abstract

Poly(dimethylsiloxane) (PDMS) elastomer coatings containing an amphiphilic hydrolyzable diblock copolymer additive were prepared and their potential as marine antifouling and antiadhesion materials was tested. The block copolymer additive consisted of a PDMS first block and a random poly(trialkylsilyl methacrylate (TRSiMA, R?=?butyl, isopropyl)-co-poly(ethyleneglycol) methacrylate (PEGMA) copolymer second block. PDMS-b-TRSiMA block copolymer additives without PEGMA units were also used as additives. The amphiphilic character of the coating surface was assessed in water using the captive air bubble technique for measurements of static and dynamic contact angles. The attachment of macro- and microorganisms on the coatings was evaluated by field tests and by performing adhesion tests to the barnacle Amphibalanus amphitrite and the green alga Ulva rigida. All the additive-based PDMS coatings showed better antiadhesion properties to A. amphitrite larvae than to U. rigida spores. Field tests provided meaningful information on the antifouling and fouling release activity of coatings over an immersion period of 23?months.     

Iodine-infused aeration for hull fouling prevention: a vessel-scale study

Biofouling is a significant economic and ecological problem, causing reduced vessel performance and increases in fuel consumption and emissions. Previous research has shown iodine vapor (I₂)-infused aeration to be an environmentally friendly method for deterring the settlement of fouling organisms. An aeration system was deployed on a vessel with hull sections coated with two types of antifoulant coatings, Intersleek^® 1100 (fouling-release) and Interspeed^® BRA-640 (ablative copper biocide), as well as an inert epoxy barrier coating, to assess the effectiveness of aeration in conjunction with common marine coatings. I₂-infused aeration resulted in consistent reductions of 80–90% in hard fouling across all three coatings. Additionally, aeration reduced the soft fouling rate by 45–70% when used in conjunction with both Intersleek^® and Interspeed^® BRA versus those coatings alone. The results of this study highlight the contribution of I₂-infused aeration as a standalone mechanism for fouling prevention or as a complement to traditional antifouling coatings.     

Poly(dimethyl siloxane) (PDMS) network blends of amphiphilic acrylic copolymers with poly(ethylene glycol)-fluoroalkyl side chains for fouling-release coatings. II. Laboratory assays and field immersion trials

Amphiphilic copolymers containing different amounts of poly(ethylene glycol)-fluoroalkyl acrylate and polysiloxane methacrylate units were blended with a poly(dimethyl siloxane) (PDMS) matrix in different proportions to investigate the effect of both copolymer composition and loading on the biological performance of the coatings. Laboratory bioassays revealed optimal compositions for the release of sporelings of Ulva linza, and the settlement of cypris larvae of Balanus amphitrite. The best-performing coatings were subjected to field immersion tests. Experimental coatings containing copolymer showed significantly reduced levels of hard fouling compared to the control coatings (PDMS without copolymer), their performance being equivalent to a coating based on Intersleek 700?. XPS analysis showed that only small amounts of fluorine at the coating surface were sufficient for good antifouling/fouling-release properties. AFM analyses of coatings under immersion showed that the presence of a regular surface structure with nanosized domains correlated with biological performance.     

The effects of nitric oxide in settlement and adhesion of zoospores of the green alga Ulva

Previous studies have shown that elevated nitric oxide (NO) reduces adhesion in diatom, bacterial and animal cells. This article reports experiments designed to investigate whether elevated NO reduces the adhesion of zoospores of the green alga Ulva, an important fouling species. Surface-normalised values of NO were measured using the fluorescent indicator DAF-FM DA and parallel hydrodynamic measurements of adhesion strength were made. Elevated levels of NO caused by the addition of the exogenous NO donor SNAP reduced spore settlement by 20% and resulted in lower adhesion strength. Addition of the NO scavenger cPTIO abolished the effects of SNAP on adhesion. The strength of attachment and NO production by spores in response to four coatings (Silastic® T2; Intersleek® 700; Intersleek® 900 and polyurethane) shows that reduced adhesion is correlated with an increase in NO production. It is proposed that in spores of Ulva, NO is used as an intracellular signalling molecule to detect how conducive a surface is for settlement and adhesion. The effect of NO on the adhesion of a range of organisms suggests that NO-releasing coatings could have the potential to control fouling.     

Investigation of the antifouling constituents from the brown alga Sargassum muticum (Yendo) Fensholt

One of the most promising alternatives to toxic heavy metal-based paints is offered by the development of antifouling coatings in which the active ingredients are compounds naturally occurring in marine organisms and operating as natural antisettlement agents. Sessile marine macroalgae are remarkably free from settlement by fouling organisms. They produce a wide variety of chemically active metabolites in their surroundings, potentially as an aid to protect themselves against other settling organisms. In this study, a dichloromethane extract from the brown seaweed Sargassum muticum was tested in situ and, after 2 months of immersion, showed less fouling organisms on paints in which the extract was included, compared to paints containing only copper after 2 months of immersion. No barnacles or mussels have been observed on the test rack. Identification by NMR and GC/MS of the effective compound revealed the abundance of palmitic acid, a commonly found fatty acid. Pure palmitic acid showed antibacterial activity at 44 μg mL⁻¹, and also inhibited the growth of the diatom Cylindrotheca closterium at low concentration (EC₅₀ = 45.5 μg mL⁻¹), and the germination of Ulva lactuca spores at 3 μg mL⁻¹. No cytotoxicity was highlighted, which is promising in the aim of the development of an environmentally friendly antifouling paint.     

Investigation of the role of hydrophilic chain length in amphiphilic perfluoropolyether/poly(ethylene glycol) networks: towards high-performance antifouling coatings

The facile preparation of amphiphilic network coatings having a hydrophobic dimethacryloxy-functionalized perfluoropolyether (PFPE-DMA; M _w = 1500 g mol^?1) crosslinked with hydrophilic monomethacryloxy functionalized poly(ethylene glycol) macromonomers (PEG-MA; M _w = 300, 475, 1100 g mol^?1), intended as non-toxic high-performance marine coatings exhibiting antifouling characteristics is demonstrated. The PFPE-DMA was found to be miscible with the PEG-MA. Photo-cured blends of these materials containing 10 wt% of PEG-MA oligomers did not swell significantly in water. PFPE-DMA crosslinked with the highest molecular weight PEG oligomer (ie PEG1100) deterred settlement (attachment) of algal cells and cypris larvae of barnacles compared to a PFPE control coating. Dynamic mechanical analysis of these networks revealed a flexible material. Preferential segregation of the PEG segments at the polymer/air interface resulted in enhanced antifouling performance. The cured amphiphilic PFPE/PEG films showed decreased advancing and receding contact angles with increasing PEG chain length. In particular, the PFPE/PEG1100 network had a much lower advancing contact angle than static contact angle, suggesting that the PEG1100 segments diffuse to the polymer/water interface quickly. The preferential interfacial aggregation of the larger PEG segments enables the coating surface to have a substantially enhanced resistance to settlement of spores of the green seaweed Ulva, cells of the diatom Navicula and cypris larvae of the barnacle Balanus amphitrite as well as low adhesion of sporelings (young plants) of Ulva, adhesion being lower than to a polydimethyl elastomer, Silastic T2.     

Bioassays and field immersion tests: a comparison of the antifouling activity of copper-free poly(methacrylic)-based coatings containing tertiary amines and ammonium salt groups

This paper focuses on the activity spectrum of three dimethylalkyl tertiary amines as potential active molecules and the corresponding ammonium salt-based antifouling (AF) paints. Bioassays (using marine bacteria, microalgae and barnacles) and field tests were combined to assess the AF activity of coatings. Bioassay results demonstrated that the ammonium salt-based paints did not inhibit the growth of microorganisms (except the dimethyldodecylammonium-based coatings) and that the tertiary amines were potent towards bacteria, diatoms, and barnacle larvae at non-toxic concentrations (therapeutic ratio, LC₅₀/EC₅₀, < 1). The results from field tests indicated that the ammonium salt-based coatings inhibited the settlement of macrofouling and the dimethylhexadecylammonium-based coatings provided protection against slime in comparison with PVC blank panels. Thus, results from laboratory assays did not fully concur with the AF activity of the paints in the field trial.     

Surface sensing and stress-signalling in Ulva and fouling diatoms – potential targets for antifouling: a review

Understanding the underlying signalling pathways that enable fouling algae to sense and respond to surfaces is essential in the design of environmentally friendly coatings. Both the green alga Ulva and diverse diatoms are important ecologically and economically as they are persistent biofoulers. Ulva spores exhibit rapid secretion, allowing them to adhere quickly and permanently to a ship, whilst diatoms secrete an abundance of extracellular polymeric substances (EPS), which are highly adaptable to different environmental conditions. There is evidence, now supported by molecular data, for complex calcium and nitric oxide (NO) signalling pathways in both Ulva and diatoms being involved in surface sensing and/or adhesion. Moreover, adaptation to stress has profound effects on the biofouling capability of both types of organism. Targets for future antifouling coatings based on surface sensing are discussed, with an emphasis on pursuing NO-releasing coatings as a potentially universal antifouling strategy.     

Adhesion and motility of fouling diatoms on a silicone elastomer

Recent demands for non-toxic antifouling technologies have led to increased interest in coatings based on silicone elastomers that ‘release’ macrofouling organisms when hydrodynamic conditions are sufficiently robust. However, these types of coatings accumulate diatom slimes, which are not released even from vessels operating at high speeds ( > 30 knots). In this study, adhesion strength and motility of three common fouling diatoms (Amphora coffeaeformis var. perpusilla (Grunow) Cleve, Craspedostauros australis Cox and Navicula perminuta Grunow) were measured on a polydimethylsiloxane elastomer (PDMSE) and acid-washed glass. Adhesion of the three species was stronger to PDMSE than to glass but the adhesion strengths varied. The wall shear stress required to remove 50% of cells from PDMSE was 17 Pa for Craspedostauros, 24 Pa for Amphora and >> 53 Pa for Navicula; the corresponding values for glass were 3, 10 and 25 Pa. In contrast, the motility of the three species showed little or no correlation between the two surfaces. Craspedostauros moved equally well on glass and PDMSE, Amphora moved more on glass initially before movement ceased and Navicula moved more on PDMSE before movement ceased. The results show that fouling diatoms adhere more strongly to a hydrophobic PDMSE surface, and this feature may contribute to their successful colonization of low surface energy, foul-release coatings. The results also indicate that diatom motility is not related to adhesion strength, and motility does not appear to be a useful indicator of surface preference by diatoms.     

Antifouling potential of Subtilisin A immobilized onto maleic anhydride copolymer thin films

The proteinaceous nature of the adhesives used by most fouling organisms to attach to surfaces suggests that coatings incorporating proteolytic enzymes may provide a technology for the control of biofouling. In the present article, the antifouling (AF) and fouling release potential of model coatings incorporating the surface-immobilized protease, Subtilisin A, have been investigated. The enzyme was covalently attached to maleic anhydride copolymer thin films; the characteristics of the bioactive coatings obtained were adjusted through variation of the type of copolymer and the concentration of the enzyme solution used for immobilization. The bioactive coatings were tested for their effect on the settlement and adhesion strength of two major fouling species: the green alga Ulva linza and the diatom Navicula perminuta. The results show that the immobilized enzyme effectively reduced the settlement and adhesion strength of zoospores of Ulva and the adhesion strength of Navicula cells. The AF efficacy of the bioactive coatings increased with increasing enzyme surface concentration and activity, and was found to be superior to the equivalent amount of enzyme in solution. The results provide a rigorous analysis of one approach to the use of immobilized proteases to reduce the adhesion of marine fouling organisms and are of interest to those investigating enzyme-containing coating technologies for practical biofouling control.     

Temporal and spatial variations in macrofouling of silicone fouling‐release coatings

Nontoxic, low surface free energy silicone coatings having reduced biofouling adhesion strength have been developed as an alternative to antifouling paints. Silicone coatings permit macrofouling to adhere; however, fouling can be removed easily by water pressure or light scrubbing. One of the current methods used to evaluate the performance of non‐toxic silicone fouling‐release coatings relies heavily on fouling coverage. The organismal community structure as well as total coverage can affect the ease of fouling removal from these coatings. This paper explores fouling coverage and organismal adhesion over time. Long‐term fouling coverage data were collected at four sites (in Massachusetts, Hawaii and Florida) using static immersion panels coated with silicone and oil‐amended silicone systems. Inter‐site differences in fouling coverage and community structure were observed for each coating. Intra‐site variation and temporal change in coverage of fouling was minimal, regardless of coating formulation. The extent of coverage was affected by the duration of immersion and the local environmental conditions; these factors may also have an impact on the foul‐release capability of the silicone coatings. Organismal adhesion data was collected in Hawaii and Florida. These adhesion measurements were used as a tool to discriminate and rank fouling release coatings.     

Drag-reducing riblets with fouling-release properties: development and testing

The manufacture and preliminary testing of a drag-reducing riblet texture with fouling-control properties is presented. The commercial fouling-release product Intersleek® 1100SR was modified to manufacture riblet-textured coatings with an embossing technology. Hydrodynamic drag measurements in a Taylor–Couette set-up showed that the modified Intersleek® riblets reduced drag by up to 6% compared to a smooth surface. Barnacle settlement assays demonstrated that the riblets did not substantially reduce the ability of Intersleek® 1100SR to prevent fouling by cyprids of Balanus amphitrite. Diatom adhesion tests revealed significantly higher diatom attachment on the riblet surface compared to smooth Intersleek® 1100SR. However, after exposure to flow, the final cell density was similar to the smooth surface. Statically immersed panels in natural seawater showed an increase of biofilm cover due to the riblets. However, the release of semi-natural biofilms grown in a multi-species biofilm culturing reactor was largely unaffected by the presence of a riblet texture.     

Colonisation and succession of marine biofilm-dwelling ciliate assemblages on biocidal antifouling and fouling-release coatings in temperate Australia

Ciliate assemblages are often overlooked, but ubiquitous components of microbial biofilms which require a better understanding. Ciliate, diatom and bacterial colonisation were evaluated on two fouling-release (FR) coatings, viz. Intersleek 970 and Hempasil X3, and two biocidal antifouling (AF) coatings, viz. Intersmooth 360 and Interspeed 5640, in Port Phillip Bay, Australia. A total of 15 genera were identified during the 10 week deployment. Intersleek 970 displayed the most rapid fouling by ciliates, reaching 63.3(± 5.9) cells cm^?2. After 10 weeks, all four coatings were extensively fouled. However, the toxicity of the AF coatings still significantly inhibited microbial fouling compared to the FR coatings. On all treatments, colonies of sessile peritrichs dominated the ciliate assemblage in the early stage of succession, but as the biofilm matured, vagile ciliates exerted more influence on the assemblage structure. The AF coatings showed selective toxic effects, causing significant differences in the ciliate species assemblages among the treatments.     

Quantitative exploration of the contribution of settlement,growth, dispersal and grazing to the accumulation of natural marine biofilms on antifouling and fouling-release coatings

The accumulation of microbial biofilms on ships’ hulls negatively affects ship performance and efficiency while also playing a role in the establishment of even more detrimental hard-fouling communities. However, there is little quantitative information on how the accumulation rate of microbial biofilms is impacted by the balance of the rates of cell settlement, in situ production (ie growth), dispersal to surrounding waters and mortality induced by grazers. These rates were quantified on test panels coated with copper-based antifouling (AF) or polymer-based fouling-release (FR) coatings by using phospholipids as molecular proxies for microbial biomass. The results confirmed the accepted modes of efficacy of these two types of coatings. In a more extensive set of experiments with only the FR coatings, it was found that seasonally averaged cellular production rates were 1.5 ± 0.5 times greater than settlement and the dispersal rates were 2.7 ± 0.8 greater than grazing. The results of this study quantitatively describe the dynamic balance of processes leading to the accumulation of microbial biofilm on coatings designed for ships’ hulls.     

Biofouling communities on test panels coated with TBT and TBT-free copper based antifouling paints

Abstract

Formation of biofouling communities on the surfaces of steel panels coated with two different TBT-free copper-based and one TBT-based antifouling paint was examined following submersion for periods of 3, 6, 9 and 12 months in Kastela Bay, Croatia. Test panels coated with Shopprimer and anticorrosive paint were used as control panels. Thirty five taxa of benthic algae and 32 taxa of benthic animals were found. Diatomeae dominated by frequency and abundance on test panels coated with antifouling paints, while the animal species Serpula vermicularis, Mytilus galloprovincialis and Balanus amphitrite amphitrite dominated the fouling communities on control panels. On panels protected by antifouling paints, low values of biomass were found compared to the very high values associated with control panels.