A method for screening antifouling paints using the CIELAB coordinates of Ectocarpus sp. under a flow-through condition.

A laboratory test with a flow-through system was designed and its applicability to testing antifouling paints of varying efficacies was investigated. Six different formulations of antifouling paints were prepared to have increased contents (0 to 40 wt%) of Cu2O. The test plates were initially aged for 45 days by rotating them at a speed of 10 knots inside a cylinder drum. A bioassay was then conducted using the alga, Ectocarpus sp., as the test species. The new bioassay for screening antifouling paints under a flow-through system was successfully established using algae affixed on substrata. The correlation between the mean values of CIELAB parameters (L*, a* and b*), the total colour difference (ΔE*), and the cell survival rate of the algae was investigated. The paint performance estimated from the bioassay was confirmed using correlation patterns between colour parameters and the algal cell survival rate.

Potential ecotoxicity of metals leached from antifouling paint particles under different salinities.

Antifouling paint particles (APPs) are residues generated during maintenance of vessels. In boat maintenance areas of South America, waste generation and disposal are not completely regulated. Therefore, APPs can enter into the aquatic environment and act as a source of contamination by metals and other biocides. Thus, the aim of the present study was to evaluate the potential ecotoxicity of the metal mixture present in APPs leached under different salinities. Therefore, the copepod Acartia tonsa was exposed to different concentrations of a leachate solution prepared by the addition of APPs (1.25g/L) in artificial saline water (salinities 5, 15 and 30). Thereafter, complexing agents (EDTA and sodium thiosulfate) were added to the experimental media in order to evaluate metal influence in APPs toxicity. APPs leachate solutions were very toxic to A. tonsa, reaching an estimated LC50 of 1% at salinities 5% and 15%, and 2% at salinity 30. The addition of the chelators in leachate solutions showed that metals are the major responsible compounds for the observed toxicity. Moreover, results from the calculated toxic units suggested a slightly synergic effect between Cu and Zn in the paint formulation. A metal speciation modelling showed that Zn was predominant as a free ion at all salinities, therefore, explaining the high leachate toxicity. Furthermore, the release of Zn was observed more at lower salinities, whereas Cu was observed at higher salinities. APPs are frequently released in estuarine systems, under conditions of salinity gradients. Therefore, navigated estuaries might be under the threat of this neglected residue.

Chemical analysis of marine microdebris pollution in macroalgae from the coastal areas of Argentina.

Marine microdebris (MDs, <5 mm) and mesodebris (MesDs, 5-25 mm), consist of various components, including microplastics (MPs), antifouling or anticorrosive paint particles (APPs), and metallic particles (Mmps), among others. The accumulation of these anthropogenic particles in macroalgae could have significant implications within coastal ecosystems because of the role of macroalgae as primary producers and their subsequent transfer within the trophic chain. Therefore, the objectives of this study were to determine the abundance of MDs and MesDs pollution in different species of macroalgae (P. morrowii, C. rubrum, Ulva spp., and B. minima) and in surface waters from the Southwest Atlantic coast of Argentina to evaluate the ecological damage. MDs and MesDs were chemically characterized using µ-FTIR and SEM/EDX to identify, and assess their environmental impact based on their composition and degree of pollution by MPs, calculating the Polymer Hazard Index (PHI). The prevalence of MDs was higher in foliose species, followed by filamentous and tubular ones, ranging from 0 to 1.22 items/g w.w. for MPs and 0 to 0.85 items/g w.w. for APPs. It was found that macroalgae accumulate a higher proportion of high-density polymers like PAN and PES, as well as APPs based on alkyd, PMMA, and PE resins, whereas a predominance of CE was observed in surrounding waters. Potentially toxic elements, such as Cr, Cu, and Ti, were detected in APPs and MPs, along with the presence of epiplastic communities on the surface of APPs. According to PHI, the presence of high hazard score polymers, such as PAN and PA, increased the overall risk of MP pollution in macroalgae compared to surrounding waters. This study provided a baseline for MDs and MesDs abundance in macroalgae as well as understanding the environmental impact of this debris and their bioaccumulation in the primary link of the coastal trophic chain.

Novel antifouling paint formulation based on Ca2​Cr2O5​ and CaMnO3​ NPs as a protective pigment.

This work focused on the preparation of novel antifouling paint based on Ca2Cr2O5 and CaMnO3 NPs as a safe protective pigment which were replaced with cuprous oxide. Three paint formulations were prepared for comparison, a blank formula without an antifouling agent (F1), a commercial antifouling formula based on 100% cuprous oxide as an antifouling agent (F2), and AF formula based on 75% Ca2Cr2O5 and CaMnO3 NPs and 25% Cu2O. The high performance and durability of the paints based on the prepared pigments were evident from their impact resistance, adhesion, pending, hardness, and chemical resistance, which were compared to the blank formula (F1). The corrosion resistance of the painted films was also investigated using the salt spray test method, and the results were promising compared to the blank and standard formulations. All painted steel plates were exposed to seawater through field tests in the Suez Canal at Port Said for up to 6 months. The results showed that the paints based on F2 and F3a, b enhanced the antifouling activity through six months of exposure. The obtained results demonstrated greater efficiency of the painted steel-based F3a than F1 and F3b, and being comparable to the standard formula (F2).

Co-occurrence of microplastics and microparticles containing Cu and Zn and other heavy metals in sea-surface microlayer in Osaka Bay, Japan.

Antifouling biocides such as Cu, Zn, and organic compounds not only inhibit adhesion of sessile organisms on ship hull but also possess toxicity to non-sessile organisms in marine environment. Thus, we firstly investigated the heavy metals and polymer types of anthropogenic microparticles (MPs) floating in the sea-surface microlayer (S-SML) in Osaka Bay. 7 types of MPs containing different metals (Cu, Cu-Zn, Zn, Ti, Sn, Ba and Fe-Mn-Ni) were found. The polymer type for 97.8 % of Cu and Cu-Zn MPs (41 samples) and 52.6 % of Zn MPs (19 samples) was acrylic resins which are widely used as binders in contemporary antifouling paints for ships; concentrations of 511-54,000 mg/kg for Cu and 95.1-13,200 mg/kg for Zn were found in these MPs. The high metal concentrations found the co-existence of acrylic polymers point towards an origin from antifouling paint particles (APPs). Furthermore, to quantify Cu and Zn concentrations in these MPs based on X-ray fluorescence spectroscopy (µ-XRF), calibration curves obtained from standard paint particles containing different Cu and Zn concentrations and different particle sizes made with similar matrix used in commercial antifouling paint were firstly established, according to which highly reliable Cu and Zn concentrations in MPs were obtained.

Qualitative and quantitative assessment of microplastics derived from antifouling paint in effluent from ship hull hydroblasting and their emission into the marine environment.

This study focused on microplastic (MP) contamination originating from ship paint, particularly during the hydroblasting of ship hull, to understand the emission characteristics of MPs into the marine environment. We evaluated paint particles generated from the hydroblasting of an ocean-going vessel based on their number, size, polymer type, and mass. Hydroblasting a vessel produced 4.3 × 1015 particles, predominantly comprising acrylic particles, 99.9 % of which were smaller than 5 mm. Of the 44.1 kg of antifouling (AF) paint particles generated, 36.5 kg consisted of particles smaller than 5 mm, with 18.2 kg being identified as plastic emissions. Furthermore, we calculated the MP emission factor (8.43 g/m2) for hydroblasting on AF paint by dividing the total emission by the wetted surface area (WSA) of the vessel. This factor was then extrapolated by multiplying it with the total WSA of global ships and their hull cleaning frequency to preliminarily estimate the annual global MP emissions. Consequently, a total of 665.6 tons of plastics was generated globally by hydroblasting, with approximately 550.2 tons of these being in the form of MPs. This study highlights the need for developing stricter regulations governing hydroblasting operations and waste disposal practices to protect marine environments from MP pollution.

Microplastic-antifouling paint particle contamination alters microbial communities in surrounding marine sediment.

Paint used to coat surfaces in aquatic environments often contain biocides to prevent biofouling, and as these coatings degrade, antifouling paint particles (APPs) end up in aquatic, and especially marine, sediments. However, it is currently unclear what further influence APPs in the sediment have on biotic communities or processes. This study investigates how a variety of commercially-available APPs effect the marine microbial community by spiking different laboratory-manufactured APPs to sediment. Following exposure for 30 and 60 days, APPs caused a clear and consistent effect on the bacterial community composition as determined by 16S metabarcoding. This effect was strongest between 0 and 30 days, but continues to a lesser extent between 30 and 60 days. APPs appear to inhibit the highly diverse, but in general rarer, fraction of the community and/or select for specific community members to become more dominant. 71 antifouling-presence and 454 antifouling-absence indicator taxa were identified by indicator analysis. The difference in the level of classification in these two indicator groups was highly significant, with the antifouling-presence indicators having much higher percentage sequence identity to cultured taxa, while the antifouling-absence indicators appear to be made up of undescribed taxa, which may indicate that APPs act as a proxy for general anthropogenic influence or that APP contamination selects for taxa capable of being cultured. Given the clear and consistent effect APPs have on the surrounding sediment microbial community, further research into how APPs affect sediment functional processes and how such effects scale with concentration is recommended to better assess the wider consequences of these pollutants for marine biogeochemical cycles in the future. SYNOPSIS: Microplastic-paint particles are commonly found in marine sediment but little is known about how these, especially antifouling, paint particles affect sediment microbial communities. This study demonstrates that antifouling paint particles fundamentally alter sediment microbial communities.

Abundance and characteristics of microplastics in the Wanquan River estuary, Hainan Island.

As the nexus where rivers and oceans meet, estuaries are vulnerable to microplastic (MP) pollution derived from rivers. However, few studies have focused on the pollution status of MPs in small estuarine areas. Here, the abundance and characteristics of MPs in surface water and sediment samples from a small estuary, the Wanquan River estuary, were studied. The average abundance of MPs was 6573 ± 2659 n/m3 in surface water and 1065 ± 696 n/kg dw in sediment samples from the Wanquan River estuary. Most of the MPs in water samples and sediments were red (92.9 % and 88.1 %) fragments (87.4 % and 95.5 %) with sizes <1.0 mm (90.8 % and 92.4 %) made up of antifouling paint particles (APPs) (83.5 % and 89.8 %), respectively. A significant positive correlation (p < 0.01) was found between the concentration of Cu2+ and the abundance of APPs in sediment samples from the Wanquan River estuary. The APPs in the sediments can act as a continuous source of toxic chemicals (e.g., Cu2+) to marine environments. The results of this study expand our knowledge about MP pollution in small estuaries, and the ecological risk of APPs in the Wanquan River estuary to aquatic organisms should not be ignored.

Effect of wastewater from the in-water cleaning of ship hulls on attached and unattached microalgae.

Environmental spills of in-water hull cleaning wastewater (HCW) containing heavy metals and biocides is inevitable, and the effects of HCW on microalgae are unknown. To investigate this, we conducted microcosm experiments by adding HCW to natural seawater. HCW samples were obtained from two different cleaning methods (soft: sponge, hard: brush), and 5 % or 10 % were added to natural seawater as treatments. Dissolved Cu concentrations were 5 to 10 times higher in the treatments than those in the control. There were significant differences in growth of unattached microalgae depending on HCW dose (chlorophyll a: 34.1 ± 0.8 µg L-1 in control vs. 12.6 ± 4.3 µg L-1 in treatments). Conversely, the biomass of attached microalgae increased with HCW dose, which was associated with most of the nutrient reduction later in the experiment, rather than unattached microalgae. Our findings suggest that HCW can significantly impact microalgal community, especially depending on spill volume.

Metals and suspended solids in the effluents from in-water hull cleaning by remotely operated vehicle (ROV): Concentrations and release rates into the marine environment.

An increase in the use of ROVs for in-water hull cleaning (IWC) has led to the need to understand the risks to the marine environment posed by the release of IWC effluents. The primary objective of this research is to investigate the characteristics of wastewater generated during IWC, specifically concerning suspended solids (SS) and metal concentrations, and their release rates and total load to the environment. The IWC effluents contain substantial amounts of SS and metals, with Cu and Zn being the most prevalent. These metals are predominantly associated with fine antifouling paint particles, posing a potential risk of secondary pollution upon release into the marine environment. While the treatment systems demonstrated effectiveness in reducing SS and particulate metals, achieving complete removal of dissolved and particulate metals below ambient levels proved to be challenging. To mitigate environmental risks, this study proposes, based on the particle size analysis, the implementation of multistage filtration systems with an optimal filtration pore size for the effluent treatment. In conclusion, we highlight the potential environmental risks of IWC activities. As most metals have a strong affinity towards particles in wastewater, effective removal of particles is essential to alleviate environmental stress at IWC sites.

Comparison of the accumulation and effects of copper pyrithione and copper sulphate on rainbow trout larvae.

Copper pyrithione (CuPT) is used as a co-biocide in new antifouling paints but its toxicity remains little known. To compare the toxicity of copper-based compounds, rainbow trout (Oncorhynchus mykiss) larvae were exposed for 8-day to CuPT and CuSO4 at equivalent copper concentrations. CuPT exposure led to the greatest accumulation of Cu in larvae. Exposure to 10 µg.L-1 CuPT induced 99% larval mortality but only 4% for CuSO4-exposed larvae. The larval development and growth were affected by CuPT (from 0.5 µg.L-1 Cu) but not by CuSO4. Lipid peroxidation was not induced by either contaminant. The expression of genes involved in oxidative stress defence, detoxification and copper transport was induced in larvae exposed to CuSO4 and CuPT but at higher concentrations for CuPT. This study highlights the marked toxicity of CuPT for early life stages of fish and raises the question of the possible environmental risks of this antifouling compound.

Anthropogenic Microparticles in Sea-Surface Microlayer in Osaka Bay, Japan.

The abundance, distribution, and composition of microparticles (MPs) in the sea-surface microlayer (S-SML, less than 100 µm of sea surface in this experiment) and in bulk water (1 m under the sea surface) were investigated to evaluate the pollution level of MPs in Osaka Bay in Japan. Both seawater fractions were collected at eight sites including ship navigation routes, the coastal area, and the center of Osaka Bay for 2021-2023. MPs were filtered for four size ranges (10-53, 53-125, 125-500, and >500 µm) and then digested with H2O2. MPs' abundance was microscopically assessed; and polymer types of MPs were identified by a Fourier transform infrared spectrometer (FTIR). For the 22 collections performed along eight sites, the average MPs' abundance was 903 ± 921 items/kg for S-SML, while for the 25 collections performed along the same sites, the average MPs' abundance was 55.9 ± 40.4 items/kg for bulk water, respectively. MPs in both S-SML and bulk water exhibited their highest abundance along the navigation routes. The smallest MPs (10-53 µm) accounted for 81.2% and for 62.2% of all MPs in S-SML and in bulk water among all sites, respectively. Polymethyl methacrylate (PMMA) was the major type of MPs identified while minor ones were polyethylene, polyesters, polystyrene, polypropylene, polyvinyl chloride, polyamide, etc. PMMA comprised 95.1% of total MPs in S-SML and 45.6% of total MPs in bulk water. In addition, PMMA accounted for 96.6% in S-SML and 49.5% in bulk water for the smallest MP category (10-53 µm). It can be assumed that the MP sources were marine paints-primarily APPs (antifouling paint particles)-as well as land coatings. Sea pollution due to microparticles from ship vessels should be given proper attention.

Remote sensing of boat abandonment using Google Earth.

Abandoned boats represent a pervasive and growing problem in the coastal zone that has received little regulatory or scientific attention. In this study, we show how Google Earth can be employed to remotely identify abandoned boats and provide information on their size, age and condition. Based on specified criteria for abandonment, a survey of southern England (1700 km in length) revealed the presence of 266 boats that were mainly located in the intertidal zones of estuaries and inlets and that were often contained within clusters. Boat length ranged from 2.6 to 60 m (median = 10.5 m), and since 2004 abandonment has been increasing at a rate of about eight per year. The majority of boats appeared to be of timber construction and exhibited evidence of damage and water-sediment ingression. The environmental impacts are likely to be most significant where boats are clustered on protected mudflats.

A baseline of copper associated with antifouling paint in marinas within a large fjord estuary.

Marinas have been shown to contribute elevated concentrations of copper (Cu) to marine waters. The Cu can come primarily from antifouling paints which are designed to discourage biofouling of boat hulls. Legislation in Washington State, USA is being developed to limit or regulate the amount and rate of diffusion of Cu from antifouling paints. This study provides baseline data for Cu in five marinas of different configuration and size within Puget Sound, a large fjord estuary. Samples were collected over a year from multiple environmental media. We find strong evidence that Cu accumulates inside marinas to higher concentrations than outside marinas. Marinas that are more enclosed accumulated higher concentrations of Cu than more open marinas. Using a power analysis, we assessed the adequacy of the baseline dataset to measure progress as a result of future legislation towards the reduction of Cu to Puget Sound from marinas.

Concentrations and risk assessment of metals and microplastics from antifouling paint particles in the coastal sediment of a marina in Simon's Town, South Africa.

Maintenance of maritime vessels includes the removal of paint from hulls that are sources of metals, antifouling paint particles (APPs) and microplastics (MPs) that end up in the coastal environment. Simon's Town is a small urban town in False Bay, Cape Town, South Africa, where maritime activities take place (there is a naval harbour, marina and shipyard). The aim of this study was to measure metals, APPs and MPs in Simon's Town, to assess the impact of maritime activities and a storm water pipe in a sheltered marina. Sediment samples were collected from six sites during winter 2018. Sediment and extracted APPs were analysed for metal concentrations (Al, As, B, Ba, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, Sb, Sn, Sr, V and Zn) and MPs characterised based on type (shape and polymer), colour and size. Highest average metal concentrations in sediment for all sites were Fe (32228 ± SEM 4024), Al (12271 ± 1062) and Cu (1129 ± 407). Metals in paint particles were highest for Fe (80873 ± 19341), Cu (66762 ± 13082) and Zn (44910 ± 1400 µg/g). Metal and MP fragment concentrations were highest at the slipway of the shipyard, decreasing with increased distance from the slipway. MP filaments were highest close to the storm water outfall pipe. Our results suggest that shipyards are potential sources of metals and MP fragments (mainly APPs), with storm water pipes potential sources of MP filaments. Various indices applied to assess the potential impacts of metals and MPs suggest that these contaminants have the potential to adversely impact the intertidal ecosystem investigated.

Mexican paradise under threat: The impact of antifouling biocides along the Yucatán Peninsula.

Levels of booster biocides (Irgarol, diuron, chlorothalonil, dichlofluanid and DCOIT), organotins (TBT, DBT, MBT, TPhT, DPhT and MPhT) and antifouling paint particles (APPs) were assessed in sediments of sites under the influence of maritime activities along the coastal zone of the Yucatán Peninsula, Mexico. Imposex incidence and organotin levels were also evaluated in seven caenogastropod species. The incidence of imposex was detected in five species from sites nearby fishing harbors and marinas, including the first reports to Gemophos tinctus and Melongena bispinosa. Butyltins levels were higher than phenyltins in gastropod tissues, sediments, and APPs. Regarding booster biocides, chlorothalonil was the most frequently detected compound and DCOIT was the most abundant biocide in sediments. DCOIT levels were registered in APPs from fishing harbors and marina areas. In addition, the highest levels of TBT, Irgarol, diuron and DCOIT exceeded the threshold limits set by international sediment quality guidelines, indicating that toxic effects could be expected in some of the studied areas, thus being a potential threat to marine life. Based on such outputs, Mexico urgently needs to adopt restrictive actions aiming at conserving the rich biological heritage of the Yucatán Peninsula.

A computational model for microbial colonization of an antifouling surface.

Biofouling of marine surfaces such as ship hulls is a major industrial problem. Antifouling (AF) paints delay the onset of biofouling by releasing biocidal chemicals. We present a computational model for microbial colonization of a biocide-releasing AF surface. Our model accounts for random arrival from the ocean of microorganisms with different biocide resistance levels, biocide-dependent proliferation or killing, and a transition to a biofilm state. Our computer simulations support a picture in which biocide-resistant microorganisms initially form a loosely attached layer that eventually transitions to a growing biofilm. Once the growing biofilm is established, immigrating microorganisms are shielded from the biocide, allowing more biocide-susceptible strains to proliferate. In our model, colonization of the AF surface is highly stochastic. The waiting time before the biofilm establishes is exponentially distributed, suggesting a Poisson process. The waiting time depends exponentially on both the concentration of biocide at the surface and the rate of arrival of resistant microorganisms from the ocean. Taken together our results suggest that biofouling of AF surfaces may be intrinsically stochastic and hence unpredictable, but immigration of more biocide-resistant species, as well as the biological transition to biofilm physiology, may be important factors controlling the time to biofilm establishment.

Legacy and emerging antifouling biocide residues in a tropical estuarine system (Espirito Santo state, SE, Brazil).

The contamination by antifouling biocide residues (booster biocides - diuron, Irgarol, chlorothalonil, dichlofluanid and DCOIT; butyltin compounds-BTs (TBT, DBT and MBT); and antifouling paint particles-APPs) was appraised in sediments of Vitoria Estuarine System (VES). Even at its historical lower (ΣBTs ≤113 ng Sn g-1 dry wt), the current environmental levels of BTs in areas with a predominance of boatyards still pose a risk to the local biota and human population. DCOIT, among booster biocides, was the most frequently detected, especially in boatyards (≤40 ng g-1 dry wt) and Vitoria Port (64 ng g-1 dry wt), while APPs were also detected mainly in sediments of boatyards (≤5,969 µg g-1 dry wt). Since levels of diuron and DCOIT in APPs were as high as 1,670,000 and 899,000 ng g-1 dry wt, respectively, they are acting as secondary sources of these antifouling biocides. Therefore, VES is threatened by antifouling biocide residues due to the multiple diffuse sources of contamination, showing the need for more efforts on public policies (including temporal trend monitoring studies).

Labile metal assessment in water by diffusive gradients in thin films in shipyards on the Brazilian subtropical coast.

Shipyards impact on estuarine environments because of the use of antifouling paints and petroleum products, which release trace metals that may remain in their bioavailable or labile form. Regardless of its importance, the relation between continuous input of trace metals (hotspot area) and their availability in the water column has been scarcely studied. This study evaluated seasonal variations in the concentrations of labile fractions of metals in shipyards located in estuarine areas on the Brazilian subtropical coast. These fractions were determined by the Diffuse Gradients in Thin Films (DGT) technique. Maximum labile fraction concentrations of Cr (0.3 µg L-1), Ni (2.2 µg L-1) and V (2.0 µg L-1) are directly related to (i) their specific source: antifouling paints (for Cr), metal and steel alloys (for Cr and Ni) and petroleum products (for V), besides (ii) periods of intensive traffic and vessel repair. Additionally, variations in labile fractions of Ni and V in the Patos Lagoon estuary were influenced by salinity, which is known to affect metal desorption from surface sediments in resuspension events. Even though Cr is affected by the same processes, it is available as Cr(III) and does not represent any ecological risk in the study areas. Although the areas under study are affected by variations in physical and chemical conditions, shipyards were effectively hotspots of trace metals in their labile fraction in various estuarine systems in southeastern and southern Brazil. Thus, they represent areas where Ecological Risk Assessment, mainly of V, should be carried out.

Accelerated weathering affects the chemical and physical properties of marine antifouling paint microplastics and their identification by ATR-FTIR spectroscopy.

Microplastics prepared from commercial marine antifouling paints were weathered by UV-C irradiation representing between 25 and 101 days of real-time, outdoor exposure. Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy of the degraded paint particles showed that weathering induced chemical changes in the material, including the release of volatile components and the formation of hydrophilic groups. The chemical changes and increased reactivity of the paint binder were associated with alterations in their physical properties and increased leaching of metals in freshwater conditions. Changes in the spectra obtained from weathered paint samples reduced their match with spectra of unaged materials, resulting in a poorer similarity index, the Score when using automatic identification tools for microplastics. The results suggest that spectra of weathered, as well as pristine paint microplastics, should be consulted when applying analytical pipelines to identify microplastics extracted from natural matrices.