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

The Authors 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

Equilibrium Sampling From Nonequilibrium Dynamics

We present some applications of an Interacting Particle System (IPS) methodology to the field of Molecular Dynamics. This IPS method allows several simulations of a switched random process to keep closer to equilibrium at each time, thanks to a selection mechanism based on the relative virtual work induced on the system. It is therefore an efficient improvement of usual non-equilibrium simulations, which can be used to compute canonical averages, free energy differences, and typical transitions paths

Phase transitions in a ferrofluid at magnetic field induced microphase separation

In the presence of a magnetic field applied perpendicular to a thin sample layer, a suspension of magnetic colloidal particles (ferrofluid) can form spatially modulated phases with a characteristic length determined by the competition between dipolar forces and short-range forces opposing density variations. We introduce models for thin-film ferrofluids in which magnetization and particle density are viewed as independent variables and in which the non-magnetic properties of the colloidal particles are described either by a lattice-gas entropy or by the Carnahan-Starling free energy. Our description is particularly well suited to the low-particle density regions studied in many experiments. Within mean-field theory, we find isotropic, hexagonal and stripe phases, separated in general by first-order phase boundaries.Comment: 12 pages, RevTex, to appear in PR

Toxic metal enrichment and boating intensity: sediment records of antifoulant copper in shallow lakes of eastern England

Tributyltin (TBT), an aqueous biocide derived from antifouling paint pollution, is known to have impacted coastal marine ecosystems, and has been reported in the sediment of the Norfolk and Suffolk Broads, a network of rivers and shallow lakes in eastern England. In the marine environment, the 1987 TBT ban has resulted in expanded use of alternative biocides, raising the question of whether these products too have impacted the Broads ecosystem and freshwaters in general. Here we examine the lake sediment record in the Norfolk and Suffolk Broads for contamination by copper (Cu) (as an active biocide agent) and zinc (Zn) (as a component of booster biocides), to assess their occurrence and potential for causing environmental harm in freshwater ecosystems. We find that, after the introduction of leisure boating, there is a statistically significant difference in Cu enrichment between heavily and lightly boated sites, while no such difference exists prior to this time. At the heavily boated sites the onset of Cu enrichment coincides with a period of rapid increase in leisure boating. Such enrichment is maintained to the present day, with some evidence of continued increase. We conclude that Cu-based antifouling has measurably contaminated lakes exposed to boating, at concentrations high enough to cause ecological harm. Similar findings can be expected at other boated freshwater ecosystems elsewhere in the world

Media events, spectacles and risky globalization: a critical review and possible avenues for future research

We review the research conducted to date on media events and media spectacles. We posit that the main phenomena challenging the current conceptualizations of media event and media spectacle are (1) the understanding of risk, (2) the context of disasters and (3) globalization and the mediation of news in the context of transnational and transitional societies. We suggest that more research on disruptive events is needed. In the context of the new media landscape in particular, the ritual researcher may need to take into account the concepts of temporality and unpredictability as inherent features of media events and rituals – the traumatic events researcher may benefit from the concept of global risk society. Finally, we argue that more research needs to be carried out on transitional societies, as we need to learn more about the role of mediation, events and spectacles in democratization processes and in contemporary revolutions. Overall, our findings indicate that in the context of global risk society, constant disruptions and unplanned events, together with the changes in news transmission, need to be taken as a starting point also in the research frames used to understand the mediation of events in contemporary society

Equilibrium molecular thermodynamics from Kirkwood sampling.

We present two methods for barrierless equilibrium sampling of molecular systems based on the recently proposed Kirkwood method (J. Chem. Phys. 2009, 130, 134102). Kirkwood sampling employs low-order correlations among internal coordinates of a molecule for random (or non-Markovian) sampling of the high dimensional conformational space. This is a geometrical sampling method independent of the potential energy surface. The first method is a variant of biased Monte Carlo, where Kirkwood sampling is used for generating trial Monte Carlo moves. Using this method, equilibrium distributions corresponding to different temperatures and potential energy functions can be generated from a given set of low-order correlations. Since Kirkwood samples are generated independently, this method is ideally suited for massively parallel distributed computing. The second approach is a variant of reservoir replica exchange, where Kirkwood sampling is used to construct a reservoir of conformations, which exchanges conformations with the replicas performing equilibrium sampling corresponding to different thermodynamic states. Coupling with the Kirkwood reservoir enhances sampling by facilitating global jumps in the conformational space. The efficiency of both methods depends on the overlap of the Kirkwood distribution with the target equilibrium distribution. We present proof-of-concept results for a model nine-atom linear molecule and alanine dipeptide.This research was funded by the European Research Council and EPSRC grant EP/I001352/1. Y.O. was supported, in part, by the JSPS Grant-in-Aid for Scientific Research on Innovative Areas (“Dynamical Ordering and Integrated Functions”).This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/acs.jpcb.5b01800

Assessment of software methods for estimating protein-protein relative binding affinities.

A growing number of computational tools have been developed to accurately and rapidly predict the impact of amino acid mutations on protein-protein relative binding affinities. Such tools have many applications, for example, designing new drugs and studying evolutionary mechanisms. In the search for accuracy, many of these methods employ expensive yet rigorous molecular dynamics simulations. By contrast, non-rigorous methods use less exhaustive statistical mechanics, allowing for more efficient calculations. However, it is unclear if such methods retain enough accuracy to replace rigorous methods in binding affinity calculations. This trade-off between accuracy and computational expense makes it difficult to determine the best method for a particular system or study. Here, eight non-rigorous computational methods were assessed using eight antibody-antigen and eight non-antibody-antigen complexes for their ability to accurately predict relative binding affinities (ΔΔG) for 654 single mutations. In addition to assessing accuracy, we analyzed the CPU cost and performance for each method using a variety of physico-chemical structural features. This allowed us to posit scenarios in which each method may be best utilized. Most methods performed worse when applied to antibody-antigen complexes compared to non-antibody-antigen complexes. Rosetta-based JayZ and EasyE methods classified mutations as destabilizing (ΔΔG < -0.5 kcal/mol) with high (83-98%) accuracy and a relatively low computational cost for non-antibody-antigen complexes. Some of the most accurate results for antibody-antigen systems came from combining molecular dynamics with FoldX with a correlation coefficient (r) of 0.46, but this was also the most computationally expensive method. Overall, our results suggest these methods can be used to quickly and accurately predict stabilizing versus destabilizing mutations but are less accurate at predicting actual binding affinities. This study highlights the need for continued development of reliable, accessible, and reproducible methods for predicting binding affinities in antibody-antigen proteins and provides a recipe for using current methods