The adhesive strategies of cyprids and development of barnacle-resistant marine coatings

Over the last decade, approaches to the development of surfaces that perturb settlement and/or adhesion by barnacles have diversified substantially. Although, previously, coatings research focussed almost exclusively on biocidal technologies and low modulus, low surface-free-energy ‘fouling-release’ materials, novel strategies to control surface colonisation are now receiving significant attention. It is timely, therefore, to review the current ‘state of knowledge’ regarding fouling-resistant surface characteristics and their mechanisms of action against settling larvae of barnacles. The role of the barnacle in marine fouling is discussed here in the context of its life cycle and the behavioural ecology of its cypris larva. The temporary and permanent adhesion mechanisms of cyprids are covered in detail and an overview of adult barnacle adhesion is presented. Recent legislation has directed academic research firmly towards environmentally inert marine coatings, so the actions of traditional biocides on barnacles are not described here. Instead, the discussion is restricted to those surface modifications that interfere with settlement-site selection and adhesion of barnacle cypris larvae; specifically, textural engineering of surfaces, development of inert ‘non-fouling’ surfaces and the use of enzymes in antifouling.     

Current and emerging environmentally-friendly systems for fouling control in the marine environment

Following the ban in 2003 on the use of tributyl-tin compounds in antifouling coatings, the search for an environmentally-friendly alternative has accelerated. Biocidal TBT alternatives, such as diuron and Irgarol 1051®,¹ have proved to be environmentally damaging to marine organisms. The issue regarding the use of biocides is that concerning the half-life of the compounds which allow a perpetuation of the toxic effects into the marine food chain, and initiate changes in the early stages of the organisms' life-cycle. In addition, the break-down of biocides can result in metabolites with greater toxicity and longevity than the parent compound.     

Natural product antifoulants: One perspective on the challenges related to coatings development

Fouling of surfaces by abiotic and biotic substances has molecular, microbial, and macro-organismal levels of organization. Fouling involves molecular bonding and biological adhesives. Existing commercial solutions to fouling are antifouling or foul-release. Antifouling uses broad-spectrum biocides which kill foulers by virtue of oxidation or toxic metal ions. Foul-release coatings are dimethyl silicone polymers that foul, but clean easily. The best foul-release coatings also contain additives that kill organisms. Environmentally unacceptable consequences of toxic antifouling coatings, especially those based on organotins, have prompted interest in antifoulants found in living organisms. Laboratories worldwide now use bioassays with target fouling organisms to direct purification and identification of antifoulant compounds. Natural antifoulants are common and include toxins, anesthetics, surface-active agents, attachment and/or metamorphosis inhibitors and repellents. Development of commercial coatings using natural products is blocked by cost, the time horizon to meet government regulations and performance standards based upon coatings with unacceptable environmental impacts. If blocks are removed, the potential for environmentally acceptable solutions that combine natural products with organic biocides is high.     

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.     

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.     

Unravelling the core microbiome of biofilms in cooling tower systems

In this study, next generation sequencing and catalyzed reporter deposition fluorescence in situ hybridization, combined with confocal microscopy, were used to provide insights into the biodiversity and structure of biofilms collected from four full-scale European cooling systems. Water samples were also analyzed to evaluate the impact of suspended microbes on biofilm formation. A common core microbiome, containing members of the families Sphingomonadaceae, Comamonadaceae and Hyphomicrobiaceae, was found in all four biofilms, despite the water of each coming from different sources (river and groundwater). This suggests that selection of the pioneer community was influenced by abiotic factors (temperature, pH) and tolerances to biocides. Members of the Sphingomonadaceae were assumed to play a key role in initial biofilm formation. Subsequent biofilm development was driven primarily by light availability, since biofilms were dominated by phototrophs in the two studied ‘open’ systems. Their interactions with other microbial populations then shaped the structure of the mature biofilm communities analyzed.     

Natural products as antifouling compounds: recent progress and future perspectives

Since early 2008, an increasing number of countries have ratified an international treaty to ban the application of antifouling (AF) coatings based on organotin compounds (eg tributyltin (TBT) and triphenyltin). As a result, the demand for environmentally friendly, non-toxic or low-toxicity AF compounds and technologies (green AF agents) has become an urgent reality. Marine coatings based on Cu₂O and various other biocides have a negative impact on the environment and they must eventually be replaced by new, effective, and environmentally friendly AF compounds. This mini-review describes important AF compounds discovered from a variety of organisms from 2004 until mid 2009, and discusses recent and general trends in the discovery of AF compounds. Finally, a perspective on the future of AF compound development is presented. The discussion is aimed at updating scientists and engineers on the current challenges facing AF research.     

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 (EC₅₀ values between 0.19 and 3.61?μg?ml^?1) and low toxicity (LC₅₀ 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.     

Biodeterioration of external architectural paint films - A review

This paper presents a review of the biodeterioration of architectural paint films by bacteria, fungi and algae, concentrating on external films. 107 references are cited in the following sections: 1. Microbiota of paint films - resident microflora, colonization and biofilm formation; 2. Effects of environment on biofilm formation and survival; 3. Influence of paint formulation on colonization - basic paint components, pigment volume content (PVC), pigments, biocides; 4. Effects of painted substrate on susceptibility; 5. Instrumental methods used in the analysis of paint film biodeterioration - vibrational spectroscopy, laser-induced breakdown spectroscopy, HPLC, image analysis, FTIR spectroscopy, GC-MS; 6. New technologies in the coatings industry - photocatalytic layers, cool paints, silver nanoparticles, silicon-containing paints.     

From Broad-Spectrum Biocides to Quorum Sensing Disruptors and Mussel Repellents: Antifouling Profile of Alkyl Triphenylphosphonium Salts

‘Onium’ compounds, including ammonium and phosphonium salts, have been employed as antiseptics and disinfectants. These cationic biocides have been incorporated into multiple materials, principally to avoid bacterial attachment. In this work, we selected 20 alkyl-triphenylphosphonium salts, differing mainly in the length and functionalization of their alkyl chains, in fulfilment of two main objectives: 1) to provide a comprehensive evaluation of the antifouling profile of these molecules with relevant marine fouling organisms; and 2) to shed new light on their potential applications, beyond their classic use as broad-spectrum biocides. In this regard, we demonstrate for the first time that these compounds are also able to act as non-toxic quorum sensing disruptors in two different bacterial models (Chromobacterium violaceum and Vibrio harveyi) as well as repellents in the mussel Mytilus galloprovincialis. In addition, their inhibitory activity on a fouling-relevant enzymatic model (tyrosinase) is characterized. An analysis of the structure-activity relationships of these compounds for antifouling purposes is provided, which may result useful in the design of targeted antifouling solutions with these molecules. Altogether, the findings reported herein provide a different perspective on the biological activities of phosphonium compounds that is particularly focused on, but, as the reader will realize, is not limited to their use as antifouling agents.     

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.     

Failure mechanism of copper antifouling coatings

Microanalytical techniques were used to study the changes on the surface and in the cross section of the copper antifouling coatings. Upon exposure a ‘slime’ layer develops on the coating surface and traps the dissolved copper ions. These ions react with the chloride and hydroxide ions in the seawater to form less soluble complexes which precipitate on the surface in a dense bluish-green layer underneath the slime layer. The leaching rate decreases during the exposure because of the accumulated insoluble green copper compounds which block the dissolution of the red Cu₂O. One of the major constituents in the green layer is CuCl₂3Cu(OH)₂. The ultimate failure of the antifouling coating is caused by the conversion of the CuCl₂3Cu(OH)₂ to an even less soluble crystalline form and by the green layer becoming more dense, thus blocking the access pores to the active layer.     

Influence of material properties and photocatalysis on phototrophic growth in multi-year roof weathering

Phototrophic growth on roofs leads to weathering and impacts their appearance. Roof tiles with various properties are available (natural clay, engobed, varnished or coated with photocatalytic TiO₂). The aim of this study was to examine the influence of materials on the development of phototrophic biofilms. Roof tiles were weathered in six climatic regions in Germany for several years. Phototrophic biomass was periodically determined by PAM-fluorometry, image analysis, and visual evaluation. Roof tiles of natural clay were the most heavily infested, while black varnished roof tiles were hardly covered with any phototrophs. This colonisation pattern was compared to water availability on roof tiles surfaces. In contrast to rough natural clay, varnished black tiles accumulated less water, dried quickly, and were rather resistant to phototrophs. The photocatalytic coating was not effective against phototrophic growth. Materials with appropriate properties may prevent phototrophic growth without biocides through reduced water absorption capacities and by avoiding radiation protected structures.     

A suggested standardised method for testing photocatalytic inactivation of aeroterrestrial algal growth on TiO2-coated glass

Aeroterrestrial green algae form conspicuous biofilms on man-made surfaces. The self-cleaning properties of photocatalytic coatings prevent their growth and can probably replace biocides. The aim of this study was to develop a laboratory method to investigate the efficiency of photocatalytic materials against algal growth. Two algal isolates (“Chlorella” luteoviridis, SAG 2196, and Coccomyxa sp., SAG 2040) functioned well as model organisms because they grew on almost all test specimens at 100% humidity and low UVA radiation. With these species, we examined algal growth prevention using photocatalytic glass. No effects on algal growth were detected, although the coated surfaces were photocatalytically active and degraded methylene blue. Because their cells are protected well against photocatalytically generated hydroxyl radicals, aeroterrestrial algae survive various stress factors. Nevertheless, the newly developed experimental design may be useful for assessing the biological function of other photocatalytic materials or stress factors.     

Bacterial Deterioration of Marble Monuments: A Case Study of the Conservation Project of Acropolis Monuments

The deterioration of the Acropolis monuments’ surface can be attributed to a combination of mechanical, physical, chemical and biological factors. The aim of this work was to investigate the potential use of biocides suitable for marble surface in order to confront the biodeterioration phenomenon due to heterotrophic bacteria. Surface bacterial populations were studied in respect to the application of three biocide agents. A significant decrease of the bacterial counts was occurred after the biocides’ application and remained less compared with the counts occurred on the untreated surfaces for more than 14 months. A gradual diminution of bacterial diversity was also observed leading to the survival of specific Gram positive strains.     

Marine antifouling performance of polymer coatings incorporating zwitterions

Zwitterionic materials display antifouling promise, but their potential in marine anti-biofouling is still largely unexplored. This study evaluates the effectiveness of incorporating small quantities (0–20% on a molar basis) of zwitterions as sulfobetaine methacrylate (SBMA) or carboxybetaine methacrylate (CBMA) into lauryl methacrylate-based coatings whose relatively hydrophobic nature encourages adhesion of the diatom Navicula incerta, a common microfouling organism responsible for the formation of ‘slime’. This approach allows potential enhancements in antifouling afforded by zwitterion incorporation to be easily quantified. The results suggest that the incorporation of CBMA does provide a relatively minor enhancement in fouling-release performance, in contrast to SBMA which does not display any enhancement. Studies with coatings incorporating mixtures of varying ratios of the cationic monomer [2-(methacryloyloxy)ethyl]trimethylammonium chloride and the anionic monomer (3-sulfopropyl)methacrylate, which offer a potentially lower cost approach to the incorporation of anionic and cationic charge, suggest these monomers impart little significant effect on biofouling.     

Acquired phototrophy stabilises coexistence and shapes intrinsic dynamics of an intraguild predator and its prey

In marine ecosystems, acquired phototrophs – organisms that obtain their photosynthetic ability by hosting endosymbionts or stealing plastids from their prey – are omnipresent. Such taxa function as intraguild predators yet depend on their prey to periodically obtain chloroplasts. We present a new theory for the effects of acquired phototrophy on community dynamics by analysing a mathematical model of this predator–prey interaction and experimentally verifying its predictions with a laboratory model system. We show that acquired phototrophy stabilises coexistence, but that the nature of this coexistence exhibits a ‘paradox of enrichment’: as light increases, the coexistence between the acquired phototroph and its prey transitions from a stable equilibrium to boom‐bust cycles whose amplitude increases with light availability. In contrast, heterotrophs and mixotrophic acquired phototrophs (that obtain  < 30% of their carbon from photosynthesis) do not exhibit such cycles. This prediction matches field observations, in which only strict ( > 95% of carbon from photosynthesis) acquired phototrophs form blooms.     

石质建筑的生物风化防治研究现状

石质建筑暴露在自然环境中不可避免地遭到各种因素的影响,其中由细菌、真菌、藻类、地衣和苔藓等引起的生物风化问题普遍存在,生物风化的长期累积效应会导致石质建筑在物理结构、化学性质和美学特征等方面发生不可逆的变化和损坏。因此,运用不同方法来减少生物对石质建筑的侵蚀是非常必要的。本文根据典型案例整理归纳了目前研究中生物风化治理的传统方法(包括热处理、激光和紫外线辐照、施用杀菌剂等)和几种新兴技术(包括物理方法和化学方法协同作用、植物提取物和纳米材料作为杀菌剂等),并对其优缺点及适用性进行了评述。本文还论述了石质建筑生物风化的防护对策和防治效果的检测方法,并对未来研究方向进行了展望,旨在为石质建筑的生物风化防治研究提供方法借鉴和参考。     

Effects of polarization in the presence and absence of biocides on biofilms in a simulated paper machine water

The antifouling potential of electric polarization combined and not combined with biocides was studied in nonsaline warm water with high organic content. Deinococcus geothermalis is a bacterium known for forming colored biofilms in paper machines and for its persistence against cleaning and chemical treatments. When D. geothermalis biofilms grown for 24 h in simulated paper machine water were exposed to cathodic or cathodically weighted pulsed polarization at least 60% (P < 0.05) of the biofilms were removed from stainless steel (AISI 316L). Biofilm removal by 25 ppm (effective substances 5-25 ppm) of oxidizing biocides (bromochloro-5,5-dimethylhydantoin, 2,2-dibromo-2-cyanoacetamide, peracetic acid) increased to 70% when combined with cathodically weighted pulsed polarization. Using a novel instrument that allows real-time detection of reactive oxygen species (ROS) we showed that the polarization program effective in antifouling generated ROS in a pulsed manner on the steel surface. We thus suggest that the observed added value of oxidative biocides combined with polarization depended on ROS. This suggestion was supported by the finding that a reductive biocide, methylene bisthiocyanate, counteracted the antifouling effect of polarization.     

The adhesive strategies of cyprids and development of barnacle-resistant marine coatings

Over the last decade, approaches to the development of surfaces that perturb settlement and/or adhesion by barnacles have diversified substantially. Although, previously, coatings research focussed almost exclusively on biocidal technologies and low modulus, low surface-free-energy 'fouling-release' materials, novel strategies to control surface colonisation are now receiving significant attention. It is timely, therefore, to review the current 'state of knowledge' regarding fouling-resistant surface characteristics and their mechanisms of action against settling larvae of barnacles. The role of the barnacle in marine fouling is discussed here in the context of its life cycle and the behavioural ecology of its cypris larva. The temporary and permanent adhesion mechanisms of cyprids are covered in detail and an overview of adult barnacle adhesion is presented. Recent legislation has directed academic research firmly towards environmentally inert marine coatings, so the actions of traditional biocides on barnacles are not described here. Instead, the discussion is restricted to those surface modifications that interfere with settlement-site selection and adhesion of barnacle cypris larvae; specifically, textural engineering of surfaces, development of inert 'non-fouling' surfaces and the use of enzymes in antifouling.