Molecular approaches to nontoxic antifouling

Summary

A consequence of environmental and human health concerns arising from the use of toxic metals in marine antifouling coatings has been to recognise the need for a nontoxic alternative to fouling control. Recent research has focused on two approaches to this problem: the development of (a) foul-release coatings that work on the principle of either low surface free energy or coating ablation, and (b) coatings that incorporate a compound(s) that is nontoxic, or at least environmentally benign, that will deter fouling. Here we discuss the nature of the fouling problem and a new technology that is emerging to address it. The use of natural marine products and of analogues to these compounds holds considerable promise and is an area of intense research. It is recognized, however, that a melding of the technologies of foul-release and foul-deterrence may be required to develop broad spectrum, nontoxic antifouling coatings. This approach may more closely reflect antifouling strategies adopted by marine organisms that maintain a foul-free surface.     

天然产物防除海洋污损生物的研究进展

天然防污剂是当前海洋污损生物防除的研究热点,本文综述了天然防污剂的种类和来源,以及天然防污剂的防除机理,并着重叙述了天然防污涂料配制时应关注的问题。     

化学生态学在海洋污损生物防除中的应用

在海洋环境中,许多海洋生物都能产生对环境无危害的、具有防污活性的次生代谢产物以保护自身的洁净,利于自身的生存.用化学生态学的方法从海洋生物中提取天然防除物质成为近年来解决海洋污损生物问题的新思路,其目标是寻找高效无毒的防污材料取代原有的对海洋环境有严重危害的化学合成防污材料.虽然目前对提取生物的次生代谢产物的防污机理还所知甚少,但不少从海洋生物中获得的天然产物已显示出良好的防污活性.要解决污损生物防污问题,还需对天然产物的作用机制、生态学效应、天然产物与涂料的结合、控制和释放及野外实验进行更加深入的研究与探讨.     

Temporal and spatial variation in the fouling of silicone coatings in Pearl Harbor, Hawaii

An antifouling or foul-release coating cannot be globally effective if it does not perform well in a range of environmental conditions, against a diversity of fouling organisms. From 1996 to 1998, the field test sites participating in the United States Navy's Office of Naval Research 6.2 Biofouling program examined global variation in the performance of 3 silicone foul-release coatings, viz. GE RTV11, Dow Corning RTV 3140, and Intersleek (International Coatings Ltd), together with a control anticorrosive coating (Ameron Protective Coatings F-150 series). At the University of Hawaii's test site in Pearl Harbor, significant differences were observed among the coatings in the rate of accumulation of fouling. The control coating failed rapidly; after 180-220 d immersion a community dominated by molluscs and sponges developed that persisted for the remainder of the experiment. Fouling of the GE and Dow Corning silicone coatings was slower, but eventually reached a similar community structure and coverage as the control coatings. The Intersleek coating remained lightly fouled throughout the experiment. Spatial variation in the structure of the community fouling the coatings was observed, but not in the extent of fouling. The rate of accumulation of fouling reflected differences among the coatings in adhesion of the tubeworm Hydroides elegans. The surface properties of these coatings may have affected the rate of fouling and the structure of the fouling community through their influence on larval settlement and subsequent interactions with other residents, predators, and the physical environment.     

Screening of Marine Algal Extracts for Anti-settlement Activities against Microalgae and Macroalgae

The ban on the use of TBT-based antifouling paints for boats under 25 m in length has lead to a search for new non-toxic antifoulants. One of the most promising alternative technologies to heavy metal based antifouling paint is the development of antifouling coatings whose active ingredients are naturally occurring compounds from marine organisms. This is based on the principle that marine organisms also face the problem of the presence of epibionts on their own surfaces. In this study, the antifouling activity of a series of aqueous, ethanolic and dichloromethane extracts from thirty algae from the North East Atlantic coast was investigated. The extracts were tested in laboratory assays against species representative of two major groups of fouling organisms, viz . macroalgae and microalgae. The activity of several extracts was comparable to that of heavy metals and biocides (such as TBTO and CuSO 4 ) currently used in antifouling paints and their lack of toxicity with respect to the larvae of oysters and sea urchins suggests a potential for novel active ingredients.     

Effectiveness of sodium benzoate as a freshwater low toxicity antifoulant when dispersed in solution and entrapped in silicone coatings

The traditional solution for preventing organisms from attaching to submerged surfaces is to apply antifouling coatings or biocides. Based on the varied defence mechanisms exhibited by biofilms, the antifoulant needs to prevent bacterial attachment during the early stages of biofilm formation. The potential of benzoic acid and sodium benzoate (NaB) as antifoulants for deterring freshwater bacterial attachment was evaluated with the antifoulants dispersed in solution or entrapped in silicone coatings. Effectiveness was based on the decrease in microbial attachment, limited toxicity, and minimum alteration of the properties of the coatings. The optimal NaB concentration when dispersed in solution, 700 mg l-1, resulted in a biofilm surface coverage of only 3.34% after four weeks. The model silicone, Sylgard 184, demonstrated a better overall performance than the commercial coating, RTV11. Sylgard 184 containing sodium benzoate had 41-52% less biofilm in comparison to the control Sylgard 184, whereas both the control and NaB-entrapped RTV11 coatings had significant biofilm coverage.     

海洋真菌抗污损活性天然产物研究

黏附于海洋船舶或人工设施表面的污损生物给人类海洋生产活动与生态环境带来诸多不利影响.将具有抗污损活性的化合物开发成防污涂料是目前防治海洋生物污损的最常用手段之一.而大量传统有机金属防污剂因其严重毒副作用被禁用,亟须开发高效、环境友好型抗污损涂料.海洋真菌能够产生大量结构新颖、作用机制独特的高效、低毒/无毒抗污损活性次级...     

Non-toxic antifouling activity of polymeric 3-alkylpyridinium salts from the Mediterranean sponge Reniera sarai (Pulitzer-Finali)

The antifouling activity and toxicity of polymeric 3-alkylpyridinium salts (poly-APS) isolated from the Mediterranean sponge Reniera sarai were studied. The activity of these natural products was compared to that of zinc and copper complexes of pyrithione, two non-persistent booster biocides successfully used in current antifouling coatings. Larvae of Balanus amphitrite (cyprids and nauplii) were used to monitor settlement inhibition and the extent to which inhibition was due to toxicity. The microalga Tetraselmis suecica and larvae of the mussel Mytilus galloprovincialis were used in toxicity bioassays. Compared to the booster biocides, poly-APS were less effective at inhibiting cyprid settlement, but their effects were non toxic and reversible, with very low toxicity against the organisms used in the toxicity bioassays. Although encouraging, these results are not enough to warrant the use of poly-APS as a potential commercial antifoulant. They however justify possible future efforts to chemically synthesize poly-APS analogues for further tests.     

Marine microbial natural products in antifouling coatings

Ecological problems associated with current antifouling technologies have increased interest in the natural strategies that marine organisms use to keep their surfaces clean and free from fouling. Bacteria isolated from living surfaces in the marine environment have been shown to produce chemicals that are potential antifoulants. Active compounds from the cells and culture supernatant of two bacterial strains, FS‐55 and NudMB50–11, isolated from surface of the seaweed, Fucus serratus, and the nudibranch, Archidoris pseudoargus, respectively, were extracted using solid phase extraction. The extracts were combined with acrylic base paint resin and assayed for antifouling activity by measuring their ability to inhibit the growth of fouling bacteria. These formulations were found to be active against fouling bacteria isolated from marine surfaces. The formulation of antifouling paints that incorporate marine microbial natural products is reported here for the first time. This is a significant advance towards the production of an environmentally friendly antifouling paint that utilises a sustainable supply of natural biodegradable compounds.     

Evaluation of the performance enhancement of silicone biofouling-release coatings by oil incorporation

In response to increased evidence of ecosystem damage by toxic antifouling paints, many researchers have developed nontoxic silicone fouling release coatings. The fouling release capability of these Systems may be improved by adding nonbonding silicone oils to the coating matrix. This idea has been tested by comparing the adhesion strength of hard- and soft-fouling organisms on a cured polydimethylsilicone (PDMS) network to that of the same network containing free polydi-methyldiphenylsilicone (PDMDPS) oil at five exposure sites in North America and Hawaii. Fouling coverage is discussed, together with the bioadhesion data, to emphasize that although these coatings foul the fouling is easily removed. The partitioning of the incorporated oil upon exposure of the coatings to a simulated marine environment containing sediment was determined. Less than 1.1 wt% of the incorporated oil was lost from the coating over one year, and the toxicity of these coatings was shown to be minimal to shrimp and fish. Brush abrasion wear was greater for coatings containing free oil, but the modulus of elasticity was not appreciably decreased by the addition of 10wt% free oil.     

The impact and control of biofouling in marine aquaculture: a review

Biofouling in marine aquaculture is a specific problem where both the target culture species and/or infrastructure are exposed to a diverse array of fouling organisms, with significant production impacts. In shellfish aquaculture the key impact is the direct fouling of stock causing physical damage, mechanical interference, biological competition and environmental modification, while infrastructure is also impacted. In contrast, the key impact in finfish aquaculture is the fouling of infrastructure which restricts water exchange, increases disease risk and causes deformation of cages and structures. Consequently, the economic costs associated with biofouling control are substantial. Conservative estimates are consistently between 5–10% of production costs (equivalent to US$ 1.5 to 3 billion yr^?1), illustrating the need for effective mitigation methods and technologies. The control of biofouling in aquaculture is achieved through the avoidance of natural recruitment, physical removal and the use of antifoulants. However, the continued rise and expansion of the aquaculture industry and the increasingly stringent legislation for biocides in food production necessitates the development of innovative antifouling strategies. These must meet environmental, societal, and economic benchmarks while effectively preventing the settlement and growth of resilient multi-species consortia of biofouling organisms.     

Pyrethroids as Promising Marine Antifoulants: Laboratory and Field Studies

Due to the regulations and bans regarding the use of traditional toxic chemicals against marine fouling organisms and the practical impediments to the commercialization of natural product antifoulants, there is an urgent need for compounds that are antifouling-active, environmentally friendly, and have a potential for commercial application. In this study, a series of common, commercially available pyrethroid products, which are generally used as environmentally safe insecticides, was evaluated for antifouling activity in the laboratory using an anti-settlement test with cyprids of the barnacle Balanus albicostatus and also in a field experiment. Laboratory assay showed that all eleven pyrethroids (namely, rich d-trans-allethrin, Es-biothrin, rich d-prallethrin, S-prallethrin, tetramethrin, rich d-tetramethrin, phenothrin, cyphenothrin, permethrin, cypermethrin, and high active cypermethrin) were able to inhibit barnacle settlement (EC₅₀ range of 0.0316 to 87.00 μg/ml) without significant toxicity. Analysis of structure–activity relationships suggested that the cyano group at the α-carbon position had a significant influence on the expression of antifouling activity in pyrethroids. In the field, the antifouling activity of pyrethroids was further confirmed, with the most potent pyrethroids being cypermethrin and high active cypermethrin, which displayed efficiency comparable with that of tributyltin. In summary, our investigation indicated that these pyrethroids have a great and practical commercial potential as antifouling agents.     

The Effects of Seaweed Secondary Metabolites on Biofouling

Antifouling activity is one poorly investigated property of seaweed natural products. To determine, in the field, whether seaweeds contain chemicals able to influence the settlement of fouling organisms, crude organic extracts from Stypopodium zonale, Dictyota menstrualis (Phaeophyceae) and Laurencia obtusa (Rhodophyceae) were incorporated at natural volumetric concentrations, into hard stable gels that served as substrata for fouling in the experiments. Fouling organisms settled at a significantly higher rate on plates treated with S. zonale extracts than on control gels, while settlement was strongly inhibited on gels containing L. obtusa extracts. Fouling on gels treated with the D. menstrualis extract was not significantly different from the fouling found on control gels. The findings suggest that the broad antifouling properties of the crude extract of L. obtusa inhibit the settlement of fouling as well as hinder the development of settled fouling species, thereby reducing the richness of species. The results imply that L. obtusa possibly harbours powerful agents that can be explored for the development of antifouling technology.     

Effect of secochiliolide acid isolated from the Patagonian shrub Nardophyllum bryoides as active component in antifouling paints

Environmental concerns about the use of toxic antifoulants have led to an increased interest in the development of new alternatives. So far, most of the antifouling natural products have been obtained from marine organisms. However, some secondary metabolites from terrestrial plants could be promising antifoulant candidates. The antifouling performance of secochiliolide acid, the main component isolated from Nardophyllum bryoides ethanolic extract, was evaluated for inclusion in rosin-based coatings.Field testing was conducted during the summer months at Mar del Plata harbor, Argentina. The results indicated that secochiliolide acid-based paints completely inhibited the settlement of Bugula neritina colonies, Polydora sp., Hydroides elegans, Corophium sp. and solitary ascidians, and also reduced the attachment of some algae as Enteromorpha intestinalis and Ectocarpus sp. In addition, a lower density and diversity of microfouling species was registered.These results highlighted the importance of terrestrial plants as a sustainable source of potential environmentally friendly antifoulants.     

Evaluation of the antifouling properties of 3-alyklpyridine compounds

One of the most promising alternative technologies to antifouling (AF) biocides based on toxic heavy metals lies in the development of natural eco-friendly biocides. The present study evaluates the AF potential of structurally different compounds containing a 3-alkylpyridine moiety. The products, namely poly 3-alkylpyridinium salts, saraine, and haminols, were either extracted or derived from natural sources (the sponges Haliclona sp. and Reniera sarai and the mollusc Haminoea fusari), or obtained by chemical synthesis. All the molecules tested showed generally good anti-settlement activity against larvae of the barnacle Amphibalanus (=Balanus) amphitrite (EC(50) values between 0.19 and 3.61 μg ml(-1) and low toxicity (LC(50) values ranging from 2.04 to over 100 μg ml(-1)) with non-target organisms. For the first time, the AF potential of a synthetic monomeric 3-alkylpyridine was demonstrated, suggesting that chemical synthesis is as a realistic way to produce large amounts of these compounds for future research and development of environmentally-friendly AF biocides.     

Antifouling enzymes and the biochemistry of marine settlement

Antifouling coatings are used extensively on marine vessels and constructions, but unfortunately they are found to pose a threat to the marine environment, notably due to content of metal-based biocides. Enzymes have repeatedly been proposed as an alternative to traditional antifouling compounds. In this review, the enzymes claimed to hold antifouling activity are classified according to catalytic functions. The enzyme functions are juxtaposed with the current knowledge about the chemistry of settlement and adhesion of fouling organisms. Specific focus will be on bacteria, microalgae, invertebrate larvae and macroalgae zoospores. Two main concepts in enzyme-based antifouling are identified: breakdown of adhesive components and catalytic production of repellent compounds in-situ. The validity of the various modes of action is evaluated and the groups of enzymes with the highest potential are highlighted.     

A new flow-through bioassay for testing low-emission antifouling coatings

Current antifouling (AF) technologies are based on the continuous release of biocides into the water, and consequently discharge into the environment. Major efforts to develop more environmentally friendly coatings require efficient testing in laboratory assays, followed by field studies. Barnacles are important fouling organisms worldwide, increasing hydrodynamic drag on ships and damaging coatings on underwater surfaces, and thus are extensively used as models in AF research, mostly in static, laboratory-based systems. Reliable flow-through test assays for the screening of biocide-containing AF paints, however, are rare. Herein, a flow-through bioassay was developed to screen for diverse low-release biocide paints, and to evaluate their effects on pre- and post-settlement traits in barnacles. The assay distinguishes between the effects from direct surface contact and bulk-water effects, which are crucial when developing low-emission AF coatings. This flow-through bioassay adds a new tool for rapid laboratory-based first-stage screening of candidate compounds and novel AF formulations.     

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 poly-dimethylsiloxane 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.     

Design and Biological Evaluation of Antifouling Dihydrostilbene Oxime Hybrids

By combining the recently reported repelling natural dihydrostilbene scaffold with an oxime moiety found in many marine antifoulants, a library of nine antifouling hybrid compounds was developed and biologically evaluated. The prepared compounds were shown to display a low antifouling effect against marine bacteria but a high potency against the attachment and growth of microalgae down to MIC values of 0.01 μg/mL for the most potent hybrid. The mode of action can be characterized as repelling via a reversible non-toxic biostatic mechanism. Barnacle cyprid larval settlement was also inhibited at low μg/mL concentrations with low levels or no toxicity observed. Several of the prepared compounds performed better than many reported antifouling marine natural products. While several of the prepared compounds are highly active as antifoulants, no apparent synergy is observed by incorporating the oxime functionality into the dihydrostilbene scaffold. This observation is discussed in light of recently reported literature data on related marine natural antifoulants and antifouling hybrids as a potentially general strategy for generation of improved antifoulants.     

Ship hull in-water cleaning and its effects on fouling-control coatings

Abstract

Today, ship hull fouling is managed through fouling-control coatings, complemented with in-water cleaning. During cleaning, coating damage and wear must be avoided, for maximum coating lifetime and reduced antifoulant release. When possible, cleaning should target early stages of fouling, using minimal forces. However, such forces, and their effects on coatings, have not yet been fully quantified. In this one-year study, minimal cleaning forces were determined using a newly-designed immersed waterjet. The results show that bi-monthly/monthly cleaning, with maximum wall shear stress up to ～1.3?kPa and jet stagnation pressure ～0.17?MPa, did not appear to cause damage or wear on either the biocidal antifouling (AF) or the biocide-free foul-release (FR) coatings. The AF coating required bi-monthly cleanings to keep fouling to incipient slime (time-averaged results), while the FR coating had a similar fouling level even without cleaning. The reported forces may be used in matching cleaning parameters to the adhesion strength of the early stages of fouling.