Cumulative environmental risk assessment of metals and polycyclic aromatic hydrocarbons from ship activities in ports.

Marine environmental risk assessments rarely consider the cumulative risk from multiple contaminants and sources. Ships give rise to a range of contaminants, originating from different onboard sources, resulting in contaminant loads to the marine environment. Here, the Ship Traffic Emission Assessment Model (STEAM), in combination with the hydrodynamic and chemical fate model MAMPEC, was used to calculate loads and predicted environmental concentrations (PECs) of metals and polycyclic aromatic hydrocarbons, in four ports. PECs were compared to the predicted no effect concentrations (PNEC) to assess environmental risk from the different onboard sources, both separately and cumulatively. The results show that three out of four ports were subject to unacceptable risk. This study highlights the importance of accounting for multiple contaminant sources when assessing the marine environmental risks of shipping and challenges the suitability of the proposed new international guidelines on how to assess risk of scrubber water discharge.

Are silicone foul-release coatings a viable and environmentally sustainable alternative to biocidal antifouling coatings in the Baltic Sea region?

To combat unwanted fouling on immersed hulls, biocidal antifouling coatings are commonly applied to vessels trafficking the Baltic Sea. Here, the efficacy, environmental sustainability and market barriers of silicone foul-release coatings (FRCs) was assessed for this region to evaluate their viability as replacements for biocidal coatings. Coated panels were exposed statically over a 1 year period at three locations in the Baltic Sea region to assess the long-term performance of a biocide-free FRC and two copper coatings. The FRC was found to perform equally well or significantly better than the copper coatings. Even though most silicone FRCs on the market are biocide-free, a review of the literature regarding toxic effects and the identity and environmental fate of leachables shows that they may not be completely environmentally benign, simply for the lack of biocides. Nonetheless, FRCs are substantially less toxic compared to biocidal antifouling coatings and their use should be promoted.

Metal and PAH loads from ships and boats, relative other sources, in the Baltic Sea.

The Baltic Sea is a sensitive environment that is affected by chemical pollution derived from multiple natural and anthropogenic sources. The overall aim of this study was to estimate the load of metals and polycyclic aromatic hydrocarbons (PAHs) from shipping and leisure boating, relative other sources, to the Baltic Sea and to identify possible measures that could lead to major reductions in the loads of hazardous substances from maritime shipping and leisure boating. The use of copper-based antifouling paints, and operation of scrubbers in open loop mode, were the two most dominant identified sources of hazardous substances to the Baltic Sea. Open loop scrubbers accounted for 8.5 % of the total input of anthracene to the sea. More than a third of the total load of copper can be reduced if copper-free antifouling paints or other biocide-free antifouling strategies are used on ships and leisure boats.

Framework for the environmental impact assessment of operational shipping.

Shipping is an important source of pollution affecting both atmospheric and aquatic environments. To allow for efficient mitigation of environmental degradation, it is essential to know the extent of the impacts of shipping in relation to other sources of pollution. Here, we give a perspective on a holistic approach to studies of the environmental impacts of operational shipping through presentation of an assessment framework developed and applied on a case of shipping in the Baltic Sea. Through transfer of knowledge and concepts, previously used in assessments of air pollution, now applied to assessments of marine pollution and underwater noise, the horizon of understanding of shipping-related impacts is significantly improved. It identifies the main areas of environmental degradation caused by shipping and potential improvements through legislation and technological development. However, as the vast majority of contaminants discharged into the sea are not routinely monitored and assessed, the links between pressure of contaminants from shipping and environmental state and impacts will not be caught in the current environmental regulatory frameworks.

Modelling spatial dispersion of contaminants from shipping lanes in the Baltic Sea.

Major sources of pollution from shipping to marine environments are antifouling paint residues and discharges of bilge, black, grey and ballast water and scrubber discharge water. The dispersion of copper, zinc, naphthalene, pyrene, and dibromochloromethane have been studied using the Ship Traffic Emission Assessment Model, the General Estuarine Transport Model, and the Eulerian tracer transport model in the Baltic Sea in 2012. Annual loads of the contaminants ranged from 10-2 tons for pyrene to 100 s of tons for copper. The dispersion of the contaminants is determined by the surface kinetic energy and vertical stratification at the location of the discharge. The elevated concentration of the contaminants at the surface persists for about two-days and the contaminants are dispersed over the spatial scale of 10-60 km. The Danish Sounds, the southwestern Baltic Sea and the Gulf of Finland are under the heaviest pressure of shipborne contaminants in the Baltic Sea.

Effects of seawater scrubbing on a microplanktonic community during a summer-bloom in the Baltic Sea.

The International Maritime Organization (IMO) has gradually applied stricter regulations on the maximum sulphur content permitted in marine fuels and from January 1, 2020, the global fuel sulphur limit was reduced from 3.5% to 0.5%. An attractive option for shipowners is to install exhaust gas cleaning systems, also known as scrubbers, and continue to use high sulphur fuel oil. In the scrubber, the exhausts are led through a fine spray of water, in which sulphur oxides are easily dissolved. The process results in large volumes of acidic discharge water, but while regulations are focused on sulphur oxides removal and acidification, other pollutants e.g. polycyclic aromatic hydrocarbons, metals and nitrogen oxides can be transferred from the exhausts to the washwater and discharged to the marine environment. The aim of the current study was to investigate how different treatments of scrubber discharge water (1, 3 and 10%) affect a natural Baltic Sea summer microplanktonic community. To resolve potential contribution of acidification from the total effect of the scrubber discharge water, "pH controls" were included where the pH of natural sea water was reduced to match the scrubber treatments. Biological effects (e.g. microplankton species composition, biovolume and primary productivity) and chemical parameters (e.g. pH and alkalinity) were monitored and analysed during 14 days of exposure. Significant effects were observed in the 3% scrubber treatment, with more than 20% increase in total biovolume of microplankton compared to the control group, and an even greater effect in the 10% scrubber treatment. Group-specific impacts were recorded where diatoms, flagellates incertae sedis, chlorophytes and ciliates increased in biovolume with increasing concentrations of scrubber water while no effect was recorded for cyanobacteria. In contrast, these effects was not observed in the "pH controls", a suggestion that other parameters/stressors in the scrubber water were responsible for the observed effects.

Valuating environmental impacts from ship emissions - The marine perspective.

Shipping is an activity responsible for a range of different pressures affecting the marine environment, air quality and human welfare. The methodology on how ship emissions impact air quality and human health are comparatively well established and used in cost-benefit analysis of policy proposals. However, the knowledge base is not the same for impacts on the marine environment and a coherent environmental and socio-economic impact assessment of shipping has not yet been made. This risk policies to be biased towards air pollution whilst trading off impacts on the marine environment. The aim of the current study was to develop a comprehensive framework on how different pressures from shipping degrade marine ecosystems, air quality and human welfare. A secondary aim was to quantify the societal damage costs of shipping due to the degradation of human welfare in a Baltic Sea case study. By adding knowledge from marine ecotoxicology and life-cycle analysis to the existing knowledge from climate, air pollution and environmental economics we were able to establish a more comprehensive conceptual framework that allows for valuation of environmental impacts from shipping, but it still omits economic values for biological pollution, littering and underwater noise. The results for the Baltic Sea case showed the total annual damage costs of Baltic Sea shipping to be 2.9 billion €2010 (95% CI 2.0-3.9 billion €2010). The damage costs due to impacts on marine eutrophication (768 million €2010) and marine ecotoxicity (582 million €2010) were in the same range as the total damage costs associated with reduced air quality (816 million €2010) and climate change (737 million €2010). The framework and the results from the current study can be used in future socio-economic assessments of ship emissions to prioritize cost efficient measures. The framework can be used globally but the damage costs presented on the marine environment are restricted to emissions on the Baltic Sea and Kattegat region as they are based on willingness to pay studies conducted on citizens around the Baltic Sea where eutrophication and emissions of chemicals are particularly threats to the state of the Baltic Sea.

Environmental risk assessment of using antifouling paints on pleasure crafts in European Union waters.

To ensure sustainable use of antifouling paints, the European Union have developed a new environmental risk assessment tool, which a product must pass prior to its placement on the market. In this new tool, environmental concentrations are predicted based on estimated release rates of biocides to the aquatic environment and risk characterization ratios are calculated in regional spreadsheets. There are currently two methods in use to predict release rates of biocides; a calculation method and a laboratory method. These methods have been believed to overestimate environmental release of biocides and therefore fixed correction factors to reduce the release rate can be applied. An alternative method, known as the XRF method, has recently been developed and used to derive field release rates from antifouling paints. The aim of this study was to review the new environmental risk assessment tool and assess how the choice of release rate method and application of correction factors impact the approval of antifouling paint products. Eight coatings were environmentally risk assessed for usage in four European marine regions; Baltic, Baltic Transition, Atlantic and Mediterranean; by applying release rates of copper and zinc determined with the different methods. The results showed none of the coatings to pass the environmental risk assessment in the Baltic, Baltic Transition and the Mediterranean if field release rates were used. In contrast, most of the coatings passed if the correction factors were applied on the release rates obtained with the calculation or laboratory method. The results demonstrate the importance of release rate method choice on the outcome of antifouling product approval in EU. To reduce the impact of antifouling paints on the marine environment it is recommended that no correction factors should be allowed in the environmental risk assessment or preferably that site-specific field release rates are used. If the regulation in the European Union (and elsewhere) continues to allow correction factors, the pressure of biocides to the environment from leisure boating will result in degradation of marine ecosystems.

Quantification of Cu and Zn in antifouling paint films by XRF.

Methods to determine the release of biocides (e.g. copper) and substances of concern (e.g. zinc) from antifouling paints are required for both the development of efficient products and their environmental risk assessment. To date, there are only two standardized methods available to estimate such release rates, but their reliability has been put into question. An alternative method, allowing determination of environmental release rates in the field of metallic or organometallic biocides by X-Ray Fluorescence (XRF), has been developed and applied in recent years. In this study, the potential for standardization of the XRF method is investigated through evaluation of its accuracy, precision and transferability between instruments. Accurate quantification of copper (Cu) and zinc (Zn) in µg cm-2, despite differences in chemical composition, was demonstrated through comparison of calibration regression slopes for ten different antifouling paints and confirmed through the measurement of validation samples. Universal antifouling paint calibration curves are proposed for the determination of Cu and Zn in thin paint films, with a prediction uncertainty of around ±130 µg/cm2 for both metals. The transferability of the method to another instrument was also demonstrated. For both analyzers, concentrations of validation samples were within 5% of those determined through wet chemical analysis. Pre-requisites and recommendations for the application of the method as well as its applicability to both short- and long-term release rate studies in the field are also presented and discussed.

Antifouling paints leach copper in excess - study of metal release rates and efficacy along a salinity gradient.

Antifouling paints are biocidal products applied to ship and boat hulls in order to prevent the growth and settlement of marine organisms, i.e. fouling. The release of biocides from the surface of the paint film act to repel or poison potential settling organisms. Currently, the most commonly used biocide in antifouling paints is cuprous oxide. In the EU, antifouling products are regulated under the Biocidal Products Regulation (BPR), which states that the recommended dose should be the minimum necessary to achieve the desired effect. For antifouling products, the dose is measured as the release rate of biocide(s) from coating. In this study, the release rates of copper and zinc from eight different coatings for leisure boats were determined through static exposure of coated panels in four different harbors located in Swedish waters along a salinity gradient ranging from 0 to 27 PSU. The results showed the release rate of copper to increase with increasing salinity. Paints with a higher content of cuprous oxide were also found to release larger amounts of copper. The coatings' ability to prevent biofouling was also evaluated and no significant difference in efficacy between the eight tested products was observed at the brackish and marine sites. Hence, the products with high release rates of copper were equally efficient as those with 4 - 6 times lower releases. These findings suggest that current antifouling paints on the market are leaching copper in excess of the effective dose in brackish and marine waters. Additionally, the results from the freshwater site showed no benefit in applying a copper-containing paint for the purpose of fouling prevention. This indicates that the use of biocidal paints in freshwater bodies potentially results in an unnecessary release of copper. By reducing the release rates of copper from antifouling paints in marine waters and restricting the use of biocidal paints in freshwater, the load of copper to the environment could be substantially reduced.

Environmental impacts of grey water discharge from ships in the Baltic Sea.

Discharge of grey water from ships is today unregulated in most sea areas, including the Baltic Sea. Annually, an estimated 5.5 million m3 grey water is emitted to the Baltic Sea with largest contribution from RoPax (4.25 million m3) and cruise ships (0.65 million m3). In total 44 different contaminants in grey water was identified and sorted into the sub categories organic compounds (28) and metals (16). Zinc and copper had the highest average concentrations with yearly inputs of 2.8 tons (zinc) and 1.5 tons (copper). 159 tons of nitrogen and 26.4 tons of phosphorus were estimated to be discharged to the Baltic Sea annually. An environmental risk assessment of contaminants, performed at a shipping lane in the Baltic Sea, showed the risk for adverse effects from grey water to be low. Nitrogen and phosphorus input from grey water contributes to 0.25% of the exceedance of, for the Baltic Sea set, eutrophication target.

Monitoring biofouling as a management tool for reducing toxic antifouling practices in the Baltic Sea.

Over two million leisure boats use the coastal areas of the Baltic Sea for recreational purposes. The majority of these boats are painted with toxic antifouling paints that release biocides into the coastal ecosystems and negatively impact non-targeted species. Regulations concerning the use of antifouling paints differ dramatically between countries bordering the Baltic Sea and most of them lack the support of biological data. In the present study, we collected data on biofouling in 17 marinas along the Baltic Sea coast during three consecutive boating seasons (May-October 2014, 2015 and 2016). In this context, we compared different monitoring strategies and developed a fouling index (FI) to characterise marinas according to the recorded biofouling abundance and type (defined according to the hardness and strength of attachment to the substrate). Lower FI values, i.e. softer and/or less abundant biofouling, were consistently observed in marinas in the northern Baltic Sea. The decrease in FI from the south-western to the northern Baltic Sea was partially explained by the concomitant decrease in salinity. Nevertheless, most of the observed changes in biofouling seemed to be determined by local factors and inter-annual variability, which emphasizes the necessity for systematic monitoring of biofouling by end-users and/or authorities for the effective implementation of non-toxic antifouling alternatives in marinas. Based on the obtained results, we discuss how monitoring programs and other related measures can be used to support adaptive management strategies towards more sustainable antifouling practices in the Baltic Sea.

Flawed risk assessment of antifouling paints leads to exceedance of guideline values in Baltic Sea marinas.

The seasonal variations of dissolved and bioavailable copper (Cu) and zinc (Zn) were studied in two recreational marinas in Sweden and Finland. The time series from the two marinas were characterized by rising concentrations during the spring boat launching, elevated concentrations all through the peak boating season, and decreasing concentrations in autumn when boats were retrieved for winter storage. This pattern shows a clear link between Cu and Zn concentrations and boating activity, with antifouling paints as the principal source. The leaching from antifouling paints was also found to significantly alter the speciation of dissolved Cu and Zn in marina waters, with an increase of the proportion of metals that may be considered bioavailable. This change in speciation, which occurred without any change in dissolved organic carbon (DOC), further increases the environmental risk posed by antifouling paints. In the Swedish marina, dissolved Cu and Zn exceed both Environmental Quality Standards (EQS) and Predicted No Effect Concentrations (PNEC), indicating that the current Swedish risk assessment (RA) of antifouling paints is failing to adequately protect the marine environment. An evaluation of the RA performance showed the underlying cause to be an underestimation of the predicted environmental concentration (PEC) by factors of 2 and 5 for Cu and Zn, respectively. For both metals, the use of inaccurate release rates for the PEC derivation was found to be either mainly (Cu) or partly (Zn) responsible for the underestimation. For Zn, the largest source of error seems to be the use of an inappropriate partitioning coefficient (KD) in the model. To ensure that the use of antifouling coatings does not adversely impact the sensitive Baltic Sea, it is thus recommended that the KD value for Zn is revised and that representative release rates are used in the RA procedure.

Effects of scrubber washwater discharge on microplankton in the Baltic Sea.

In 2020, the global cap of maximum allowable sulphur content in marine fuel will be reduced from the current 3.5% to 0.5%. Another way to reduce the sulphur emissions is to install a seawater scrubber that cleans exhausts but instead release acidic water containing nutrients and contaminants back to the marine environment. In the current study, scrubber washwater was tested on a Baltic Sea microplankton community. A significant increase in chlorophyll a, particulate organic phosphorus (POP), carbon (POC) and nitrogen (PON) were observed when the community was exposed to 10% scrubber washwater for 13 days as compared to the control. A laboratory experiment with the filamentous cyanobacteria Nodularia spumigena and the chain-forming diatom Melosira cf. arctica showed negative responses in photosynthetic activity (EC10 = 8.6% for N. spumigena) and increased primary productivity (EC10 = 5.5% for M. cf. arctica), implying species-specific responses to scrubber washwater discharge.

Identification of commercial and recreational vessels coated with banned organotin paint through screening of tin by portable XRF.

The most effective biocide used historically in antifouling paints is tributyltin (TBT). However, due to its extreme toxicity to non-target organisms and its persistence in the environment, the use of TBT and other organotin compounds (OTCs) was restricted in EU on leisure boats and ships in 1989 and 2003, respectively. Nevertheless, studies worldwide still report TBT to be released from both ships and leisure boats. Here, we present a new application for a field portable X-ray fluorescence spectrometer (XRF) used for screening for organotin paint through measurements of tin (Sn) on leisure boats and ships. Measurements on ships built after the restrictions showed concentrations of up to 68 µg Sn/cm2, likely due to impurities of inorganic Sn, as shown through chemical analysis of 21 organotin-free paints. A threshold value of 100 µg Sn/cm2 is suggested, where exceedance indicates presence of OTCs. Screening with the XRF method showed 10% of the commercial vessels (n = 30) and 23-29% of leisure boats (n = 693, investigated in this and in a previous study) to hold concentrations exceeding 100 µg Sn/cm2. The XRF technique presented here provides a useful tool for quick screening and identification of vessels holding banned organotin paint.

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.

In situ release rates of Cu and Zn from commercial antifouling paints at different salinities.

Antifouling paints are environmentally risk assessed based on their biocidal release rates to the water phase. In situ release rates of copper (Cu) and zinc (Zn) were derived for five commercial paints in two recreational marinas with different salinities (5 and 14 PSU) using an X-Ray Fluorescence spectrometer (XRF). Salinity was found to significantly affect the Cu release, with twice the amount of Cu released at the higher salinity, while its influence on the Zn release was paint-specific. Site-specific release rates for water bodies with salinity gradients, e.g. the Baltic Sea, are therefore necessary for more realistic risk assessments of antifouling paints. Furthermore, the in situ release rates were up to 8 times higher than those generated using standardized laboratory or calculation methods. The environmental risk assessment repeated with the field release rates concludes that it is questionable whether the studied products should be allowed on the Swedish market.

A novel XRF method to measure environmental release of copper and zinc from antifouling paints.

The release of copper (Cu) and zinc (Zn) from vessels and leisure crafts coated with antifouling paints can pose a threat to water quality in semi-enclosed areas such as harbors and marinas as well as to coastal archipelagos. However, no reliable, practical and low-cost method exists to measure the direct release of metals from antifouling paints. Therefore, the paint industry and regulatory authorities are obliged to use release rate measurements derived from either mathematical models or from laboratory studies. To bridge this gap, we have developed a novel method using a handheld X-Ray Fluorescence spectrometer (XRF) to determine the cumulative release of Cu and Zn from antifouling paints. The results showed a strong linear relationship between XRF Kα net intensities and metal concentrations, as determined by ICP-MS. The release of Cu and Zn were determined for coated panels exposed in harbors located in the Baltic Sea and in Kattegat. The field study showed salinity to have a strong impact on the release of Cu, i.e. the release increased with salinity. Contrary, the effect of salinity on Zn was not as evident. As exemplified in this work, the XRF method also makes it possible to identify the governing parameters to the release of Cu and Zn, e.g. salinity and type of paint formulation. Thus, the XRF method can be used to measure environmentally relevant releases of metallic compounds to design more efficient and optimized antifouling coatings.

Total tin and organotin speciation in historic layers of antifouling paint on leisure boat hulls.

Despite their ban on small vessels in 1989 in the EU, organotin compounds (OTCs) are still being released into the environment due to their presence in historic paint layers on leisure boats. 23 paint samples scraped from recreational boats from three countries around the Baltic Sea were analyzed for total tin (Sn) and OTCs. Two antifouling paint products were also subjected to the same analyses. A new method for the detection of Sn in paint flake samples was developed and found to yield more accurate results compared to four different acid digestion methods. A new method was also developed for the extraction of OTCs from ground paint flakes. This endeavor revealed that existing methods for organotin analysis of sediment may not have full recoveries of OTCs if paint flakes are present in the sample. The hull paint samples had Sn concentrations ranging from 25 to 18,000 mg/kg paint and results showed that tributyltin (TBT) was detected in all samples with concentrations as high as 4.7 g (as Sn)/kg paint. TBT was however not always the major OTC. Triphenyltin (TPhT) was abundant in many samples, especially in those originating from Finland. Several other compounds such as monobutyltin (MBT), dibutyltin (DBT), tetrabutyltin (TeBT), monophenyltin (MPhT) and diphenyltin (DPhT) were also detected. These could be the result of degradation occurring on the hull or of impurities in the paint products as they were also identified in the two analyzed paint products. A linear correlation (r2 = 0.934) was found between the total tin content and the sum of all detected OTCs. The detection of tin can therefore be used to indicate the presence of OTCs on leisure boats.

XRF measurements of tin, copper and zinc in antifouling paints coated on leisure boats.

Tributyltin (TBT) and other organotin compounds have been restricted for use on leisure boats since 1989 in the EU. Nonetheless, release of TBT is observed from leisure boats during hull maintenance work, such as pressure hosing. In this work, we used a handheld X-ray Fluorescence analyser (XRF) calibrated for antifouling paint matrixes to measure tin, copper and zinc in antifouling paints coated on leisure boats in Sweden. Our results show that over 10% of the leisure boats (n = 686) contain >400 µg/cm(2) of tin in their antifouling coatings. For comparison, one layer (40 µm dry film) of a TBT-paint equals ≈ 800 µg Sn/cm(2). To our knowledge, tin has never been used in other forms than organotin (OT) in antifouling paints. Thus, even though the XRF analysis does not provide any information on the speciation of tin, the high concentrations indicate that these leisure boats still have OT coatings present on their hull. On several leisure boats we performed additional XRF measurements by progressively scraping off the top coatings and analysing each underlying layer. The XRF data show that when tin is detected, it is most likely present in coatings close to the hull with several layers of other coatings on top. Thus, leaching of OT compounds from the hull into the water is presumed to be negligible. The risk for environmental impacts arises during maintenance work such as scraping, blasting and high pressure hosing activities. The data also show that many boat owners apply excessive paint layers when following paint manufacturers recommendations. Moreover, high loads of copper were detected even on boats sailing in freshwater, despite the more than 20 year old ban, which poses an environmental risk that has not been addressed until now.