Life cycle contributions of copper from vessel painting and maintenance activities

Copper-based epoxy and ablative antifouling painted panels were exposed in natural seawater to evaluate environmental loading parameters. In situ loading factors including initial exposure, passive leaching, and surface refreshment were measured utilizing two protocols developed by the US Navy: the dome method and the in-water hull cleaning sampling method. Cleaning techniques investigated included a soft-pile carpet and a medium duty 3M^? pad for fouling removal. Results show that the passive leach rates of copper peaked three days after both initial deployment and cleaning events (CEs), followed by a rapid decrease over about 15 days and a slow approach to asymptotic levels on approximately day 30. Additionally, copper was more bioavailable during a CE in comparison to the passive leaching that immediately followed. A paint life cycle model quantifying annual copper loading estimates for each paint and cleaning method based on a three-year cycle of painting, episodic cleaning, and passive leaching is presented.     

Estimates of environmental loading from copper alloy materials

Abstract

Metal release rates were measured from four different copper alloy-based materials used by the aquaculture industry: copper sheet machined into a diamond mesh, copper alloy mesh (CAM), silicon bronze welded wire mesh, and copper sheeting, and compared with conventional nylon aquaculture net treated with a cuprous oxide antifouling (AF) coating. Release rates were measured in situ in San Diego Bay using a Navy-developed Dome enclosure system at nine different time points over one year. As expected, copper was the predominant metal released, followed by zinc and nickel, which were fractional components of the materials tested. Release rates followed a temporal trend similar to those observed with copper AF coatings applied to vessel hulls: an initial spike in copper release was followed by a decline to an asymptotic low. Leachate toxicity was consistent with prior studies and was directly related to the metal concentrations, indicating the alloys tested had no additional toxicity above pure metals.     

Presence and effects of marine microbial biofilms on biocide-based antifouling paints

Marine microorganisms are capable of successfully colonizing toxic surfaces through the formation of biofilm structures. In this article, most of the literature reporting the presence of marine biofilms on chemically-active antifouling paints is briefly reviewed. Of special concern is the influence of the dense extracellular polymeric substances (EPS) matrix on the release rate of the compounds involved in antifouling paint performance (i.e. active compounds and controlled-release binder molecules). A deeper understanding of these phenomena is of interest for both environmental legislators and paint formulators.     

Presence and effects of marine microbial biofilms on biocide-based antifouling paints

Abstract

Marine microorganisms are capable of successfully colonizing toxic surfaces through the formation of biofilm structures. In this article, most of the literature reporting the presence of marine biofilms on chemically-active antifouling paints is briefly reviewed. Of special concern is the influence of the dense extracellular polymeric substances (EPS) matrix on the release rate of the compounds involved in antifouling paint performance (i.e. active compounds and controlled-release binder molecules). A deeper understanding of these phenomena is of interest for both environmental legislators and paint formulators.     

Copper release rate needed to inhibit fouling on the west coast of Sweden and control of copper release using zinc oxide

How zinc oxide influences copper release has been tested and the lowest release rate of copper from various combinations of copper and zinc in a paint matrix evaluated, whilst still deterring macrofouling, including barnacles and bryozoans. Copper (I) oxide was added to a generic AF paint in 0, 8.5, 11.7 or 16.3 wt% copper oxide in combination with 0, 10 or 20 wt% zinc oxide and applied on PMMA panels. The results show that zinc influences the release rate of copper. When 10 and 20 wt% zinc was added, the total amount of copper released significantly increased by on average 32 and 47% respectively. All treatments that included copper were successful in deterring macrofouling, including the treatment with the lowest average Cu release rate, ie 4.68 μg cm^?2 day^?1.     

The environmental fate and behaviour of antifouling paint booster biocides: A review

Antifouling paint booster biocides are a group of organic compounds added to antifouling paints to improve their efficacy. They have become prevalent since the requirement for alternative antifouling paints formulations for small boats (< 25 m). This need followed a ban on the use of triorganotin biocides in antifouling paints for small boats, in the late 1980's. Worldwide, around eighteen compounds are currently used as antifouling biocides, viz. benzmethylamide, chlorothalonil, copper pyrithione, dichlofluanid, diuron, fluorofolpet, Irgarol 1051, Sea‐Nine 211, Mancozeb, Polyphase, pyridine‐triphenyl‐borane, TCMS (2,3,5,6‐tetrachloro‐4‐methylsulfonyl) pyridine, TCMTB [2‐(thiocyanomethylthio)benzothia‐zole], Thiram, tolyfluanid, zinc pyrithione (ZPT), ziram and Zineb. Any booster biocide released into the environment is subjected to a complex set of processes. These processes include transport mechanisms, transformation, degradation, cross media partitioning, and bioaccumulation. This paper reviews the fate and behaviour data currently available in the public domain concerning antifouling paint booster biocides.     

Ultrastructural observations on the marine fouling diatomAmphora

Ecological and Scanning electron microscope (S. E. M.) studies indicated that the diatomAmphora was an important constituent in the initial colonization of test panels coated with a copper antifouling composition.Amphora was also found as the dominant fouling diatom species on paint samples from in-service supertankers and yachts. Associated with the diatom was copious amounts of mucilaginous material, which often encapsulated the cells. Histochemical analysis of the mucilage indicates that it is predominantly polysaccharide in nature. Using the Transmission electron microscope (T. E. M.) and electron microscope cytochemistry the intracellular origin of the adhesive was investigated. T. E. M. and S. E. M. observations of acid-cleaned-cells indicate that the mucilage may be secreted through specialized regions of the frustule. Material isolated from antifouling panels was compared with laboratory culturedAmphora spp. for copper resistance and internal accumulation using TEMSCAN — X ray analytical equipment.     

Differential effects of tributyltin and copper antifoulants on recruitment of non-indigenous species

Maritime transport is a primary vector for many marine invaders. For the past two decades, most commercial vessels have used tributyltin (TBT) antifouling (AF) paint, whereas recreational vessels have been restricted to alternatives, most commonly containing copper. Settlement plates painted with a collar of copper or TBT AF paint, and unpainted control plates, were deployed in commercial and recreational embayments in Port Jackson, Australia, and sampled photographically after 5 and 10 months. Copper enhanced early recruitment of several non-indigenous species (NIS), whereas recruitment of indigenous species was typically reduced by copper. TBT limited the recruitment of NIS for just 5 months and indigenous species, for the entire study. The results suggest that the use of toxic AF paints, and the possible accumulation of AF biocides in embayments, may be negatively affecting indigenous epibiota. Conversely, copper antifoulants on recreational vessels may be facilitating the transport and establishment of copper tolerant NIS into disturbed estuarine habitats.     

基于ISO 14046的工业产品水足迹评价研究——以电缆为例

水足迹国际标准(ISO 14046)于2014年发布,基于生命周期评价(LCA)的思想,水足迹被定义为量化与水相关潜在环境影响的指标。在ISO14046的原则、要求和方法学框架基础上,介绍了工业产品水足迹的计算和评价方法,并以铜电缆和铝合金电缆为例进行研究,分别评价了两类电缆生命周期过程产生的与水相关环境影响。与水足迹网络(WFN)的方法侧重于计算生产产品所需要的水资源总量不同,ISO的方法更关注于产品全生命周期过程的环境影响评价。案例研究表明:铜电缆生命周期全过程耗水量与铝合金电缆相比少24.8%,水短缺足迹相比则少97.9%。这是因为铜电缆生产地江苏的水压力指数(WSI)小于铝合金电缆生产地河北的WSI。由此,在江苏地区生产电缆使用的水资源对当地水环境压力造成的影响远小于在河北地区生产电缆造成的影响。采用科学合理的水足迹评价方法,量化工业产品全生命周期带来的环境影响,能为我国实现工业布局的合理规划和水资源的可持续利用提供科学依据。     

Minimum effective release rate of antifoulants (2): Measurement of the effect of TBT and zosteric acid on hard fouling

A membrane perfusion device for determining minimum effective release rates (MERR) of antifouling agents is described. The technique is applied to known biocidal agents and to a new prospective natural antifouling agent. This method allows controlled and reproducible release rates to be achieved independent of water chemistry and flow near the immersed surface. Unlike constant concentration methods, the device acts similarly to a painted surface, allowing establishment of diffusion gradients, thereby allowing fouling organisms to exhibit natural chemotactic responses to the released toxin. The method was applied at four remote sites to natural populations of fouling organisms. The MERRs of known (tributyltin chloride, dibutyltin chloride, and cupric ion) and experimental (zosteric acid) AF agents were determined. The effective release rates of cupric ion and organotin were consistent with immersed panel data and field observation of ship hulls, while the effective rate of zosteric acid, determined at two test sites, was much higher. Such data provide coatings formulators with valuable information relating to the suitability of an agent for AF coating use.     

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.     

A methodology for evaluating biocide release rate, surface roughness and leach layer formation in a TBT-free, self-polishing antifouling coating

Due to the forthcoming IMO ban on the use of tributyltin (TBT) antifouling paints, a new generation of TBT-free coatings has been developed that typically contain cuprous oxide and an organic co-biocide. Accurate and reproducible test methods are needed to evaluate the performance and environmental impact of these new coatings. This study investigated a methodology for evaluating TBT-free, AF coatings containing cuprous oxide. A commercially available AF coating underwent rotary immersion testing at 0, 0.51 and 2.05 m s-1. Scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) analysis were used to assess leach layer formation, percentage cuprous oxide by weight and particle size distribution (PSD). Biocide release rates and surface roughness were also measured. An increase in rotary speed caused a spike in Cu2+ release rate after which the release rate stabilised to previous levels. An increase in leach layer thickness was also observed after the rotary speed increase. A model is suggested to account for the observations.     

Thermal history regulates methylbutenol basal emission rate in Pinus ponderosa

Methylbutenol (MBO) is a 5-carbon alcohol that is emitted by many pines in western North America, which may have important impacts on the tropospheric chemistry of this region. In this study, we document seasonal changes in basal MBO emission rates and test several models predicting these changes based on thermal history. These models represent extensions of the ISO G93 model that add a correction factor C(basal), allowing MBO basal emission rates to change as a function of thermal history. These models also allow the calculation of a new emission parameter E(standard30), which represents the inherent capacity of a plant to produce MBO, independent of current or past environmental conditions. Most single-component models exhibited large departures in early and late season, and predicted day-to-day changes in basal emission rate with temporal offsets of up to 3 d relative to measured basal emission rates. Adding a second variable describing thermal history at a longer time scale improved early and late season model performance while retaining the day-to-day performance of the parent single-component model. Out of the models tested, the T(amb),T(max7) model exhibited the best combination of day-to-day and seasonal predictions of basal MBO emission rates.     

Study of erodable paint properties involved in antifouling activity

To produce ecological marine paints, it is necessary to understand the phenomena involved in antifouling activity. Due to the multivariable components which have to be taken into account and due to their analytical intricacy, only studies based on selected properties are conceivable. In this study, four properties have been chosen, viz. erosion, biocide release, roughness and the physicochemical characteristics of the film surface. A principal-component analysis (PCA) of the experimental data has shown that, among the selected properties, only erosion affected antifouling efficiency. A more detailed investigation of erosion by quantifying global hydration and hydrolysis of immersed paints revealed the difficulty in linking the chemical structure of binders to the final erosion properties. Biocide release from paints, quantified by chromatographic methods coupled with UV detection, was inferior to the doses stated by the paint producers. These observations allowed the conceiving of formulations with reduced amounts of active molecules. The development of erodable, biodegradable binders associated with non toxic compounds is a promising way to obtain efficient antifouling paints compatible with existing, preventive systems.     

新型海洋防污剂应用组分的简述

海洋防污涂料是通过海洋防污剂的可控释放,与海洋污损生物发生作用,从而阻止海生物在物体表面附着。海洋防污涂料中最重要的组成部分是基体树脂和海洋防污剂。海洋防污剂主要是从农药、杀虫剂、杀菌剂、防霉剂以及带有生物活性的聚合物中筛选出来的,随着海洋环境保护日益严格,制备和筛选高效、广谱的海洋防污剂对海洋防污涂料的发展日显重要,本文对现有的防污剂材料作了简述。     

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

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.     

A methodology for evaluating biocide release rate,surface roughness and leach layer formation in a TBT-free,self-polishing antifouling coating

Abstract

Due to the forthcoming IMO ban on the use of tributyltin (TBT) antifouling paints, a new generation of TBT-free coatings has been developed that typically contain cuprous oxide and an organic co-biocide. Accurate and reproducible test methods are needed to evaluate the performance and environmental impact of these new coatings. This study investigated a methodology for evaluating TBT-free, AF coatings containing cuprous oxide. A commercially available AF coating underwent rotary immersion testing at 0, 0.51 and 2.05 m s^?1. Scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) analysis were used to assess leach layer formation, percentage cuprous oxide by weight and particle size distribution (PSD). Biocide release rates and surface roughness were also measured. An increase in rotary speed caused a spike in Cu²⁺ release rate after which the release rate stabilised to previous levels. An increase in leach layer thickness was also observed after the rotary speed increase. A model is suggested to account for the observations.     

Computation of Operational and Environmental Benchmarks Within Selected Galician Fishing Fleets

Increasing the eco‐efficiency of fishing fleets is currently a major target issue in the seafood sector. This objective has been influenced in recent years by soaring fuel prices, a fact particularly relevant to a sector whose vessels present high energy consumption rates. Efforts to minimize fuel consumption in fishing fleets result in economic benefits and also in important reductions regarding environmental impacts. In this article, we combine life cycle assessment (LCA) and data envelopment analysis (DEA) to jointly discuss the operational and environmental performances of a set of multiple, similar entities. We applied the “five‐step LCA + DEA method” to a wide range of vessels for selected Galician fisheries, including deep‐sea, offshore, and coastal fleets. The environmental consequences of operational inefficiencies were quantified and target performance values benchmarked for inefficient vessels. We assessed the potential environmental performance of target vessels to verify eco‐efficiency criteria (lower input consumption levels, lower environmental impacts). Results revealed the strong dependence of environmental impacts on one major operational input: fuel consumption. The most intensive fuel‐consuming fleets, such as deep sea trawling, were found to entail the diesel consumption levels nearest to the efficiency values. Despite the reduced environmental contributions linked to other operational inputs, such as hull material, antifouling paint, or nets, these may contribute to substantial economic savings when minimized. Finally, given that Galicia is a major fishing region, many of the conclusions and perspectives obtained in this study may be extrapolated to other fishing fleets at the international level.     

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.     

Sediment challenge to promising ultra-low fouling hydrophilic surfaces in the marine environment

Hydrophilic coatings exhibit ultra-low fouling properties in numerous laboratory experiments. In stark contrast, the antifouling effect of such coatings in vitro failed when performing field tests in the marine environment. The fouling release performance of nonionic and zwitterionic hydrophilic polymers was substantially reduced compared to the controlled laboratory environment. Microscopy and spectroscopy revealed that a large proportion of the accumulated material in field tests contains inorganic compounds and diatomaceous soil. Diatoms adhered to the accumulated material on the coating, but not to the pristine polymer. Simulating field tests in the laboratory using sediment samples collected from the test sites showed that incorporated sand and diatomaceous earth impairs the fouling release characteristics of the coatings. When exposed to marine sediment from multiple locations, particulate matter accumulated on these coatings and served as attachment points for diatom adhesion and enhanced fouling. Future developments of hydrophilic coatings should consider accumulated sediment and its potential impact on the antifouling performance.