Multidimensional risk analysis of antifouling biocides

In order to improve the orientation about the long-term sustainability of the use of the antifouling biocides tributyltin (TBT), copper, Irgarol® 1051, Sea-Nine? 211 and zinc pyrithione, used for the protection of fouling in sea-going ships, the risks posed to the marine biosphere due to their use are evaluated. The newly presented method of risk analysis uses release rate, spatiotemporal range, bioaccumulation, bioactivity and uncertainty as 5 dimensions of ecotoxicological risk. For each dimension, a scoring procedure is briefly described. The resulting risk profiles of the antifouling biocides show characteristics of the different substances, but also indicate where further information is required. Application of the method is proposed as a decision support in the integrated development of products, informed purchasing and for regulatory purposes.     

Efficacy and toxicity of self-polishing biocide-free antifouling paints

The ban on harmful substances in antifouling paints requires the development of new antifouling strategies. Alternatives should be as effective as conventional paints but of lower toxicity. In the present study two commercially available, self-polishing antifouling paints were examined in order to get information on their antifouling properties and toxicological potential. Efficacy was shown in settlement assays with the marine barnacle species Balanus amphitrite, however, efficacy was related to toxic effects observed on target and non-target organisms. Toxicity of the paint extracts was concentration-dependent and differed according to the paint and the species investigated. Toxicity could at least partially be attributed to zinc leached from the paints. Effects of a water-soluble paint were more pronounced in larvae of B. amphitrite, Artemia salina and in the green algae Dunaliella tertiolecta. Embryos of the freshwater species Danio rerio and Vibrio fisheri were more affected by a paint based on organic solvents.     

Increased persistence of antifouling paint biocides when associated with paint particles

Current regulatory risk assessment procedures only assess the impact of antifouling paint biocides that are released through leaching from a painted surface. Hull cleaning activities can lead to particles of antifouling paint containing biocides to enter the environment. Comparative pseudo-first order anaerobic degradation rate constants and half-lives were determined for a selection of common antifouling paint booster biocides, their degradation products, and associated with paint particles. Anaerobic half-lives of <0.5 days were calculated for chlorothalonil, dichlofluanid, and SeaNine 211, between 1 and 3 days for DCPMU and DCPU, between 14 and 35 days for diuron and CPDU, and over 226 days for GS26575 and Irgarol 1051. Increased persistence was observed when the compounds were introduced to sediments associated with antifouling paint particles. When present as antifouling paint particles, an increased half-life of 9.9 days for SeaNine 211 and 1.4 days was calculated for dichlofluanid, no significant degradation was observed for diuron. It is suspected that this is due to much of the biocide being initially bound within the matrix of the paint particle that is slowly released through dissolution processes into the sediment pore water prior to degradation. The release of booster biocides associated with paint particles into marinas has the potential to lead to their accumulation unless activities such as hull cleaning are strictly regulated.     

Risk assessment of biocides in roof paint

BACKGROUND, AIM AND SCOPE: Many surface coatings, including roof paints, contain biocides. It is generally not known to what extent roof paint biocides leach from the paint, and consequently, what concentration the biocide may attain in a rainwater collection system. To this end the leaching of specific biocides from a variety of German roof paints was investigated and the resulting concentrations in collected rain water were estimated. MATERIALS AND METHODS: A laboratory simulation was used to determine the time dependant leaching rate of the biocide from the paint into synthetic rainwater. The concentrations of biocide in the leachate were quantified using HPLC. The course of the leachate concentrations over time was fitted using a simple mathematical model. This was then used to estimate concentrations of biocides in a typical household rainwater collection system over time. RESULTS: Surprisingly, the biocides found in the paints did not always concur with the declared biocides. Concerning the modelling of runoff concentrations, it was found that--under the model assumptions--the rain intensity and cumulative raining time after application are the dominant factors influencing the concentration of the biocide. At the highest modelled rain intensity of 40 mm/hour it only takes about 2 hours to reach peak concentrations lower than 0.1 mg/L, at 0.3 mm/hour it takes about 10 hours to reach peak concentrations of 1.3, 0.9, 5.2 and 1.1 mg/L for terbutryn from Emalux paint, terbutryn from Südwest paint, carbendazim from Emalux paint, and carbendazim from MIPA paint, respectively. DISCUSSION: The results confirm that biocides leached from roof paint will be present in roof runoff. The highest estimated peak concentrations are close to the water solubility of the respective biocides. This indicates that the model assumption of a concentration independent leaching rate will tendentially lead to an overestimation of the leached concentrations under these circumstances. However, under most circumstances such as higher rain intensities, and longer time after peak concentrations have been reached, the runoff concentrations are far from the solubility limit, and therefore it is proposed that the model assumptions are tenable. CONCLUSIONS: The leaching of biocides from roof paints can be roughly assessed using a relatively simple approach. The declaration of biocidal ingredients in roof paints should be improved and information on their biocide leaching behaviour should be made available. Furthermore, the estimations should be evaluated by a field study. RECOMMENDATIONS AND PERSPECTIVES: The leaching study indicated that the concentrations of selected biocides can reach significant levels, especially after low intensity rainfall. Taking into account the inherent biological activity of the substances under scrutiny, it can already be concluded that it is not advisable to use runoff water from roofs freshly painted with biocide containing roof paints. These results have been complemented by a literature search of biological effects of the investigated biocides, ecotoxicological tests with several species and a risk analysis for organisms exposed to runoff water. This will be presented in Part 2 of this contribution.     

Survey for the occurrence of antifouling paint booster biocides in the aquatic environment of Greece

Since the restriction imposed by European Union regulations on the use of TBT-based antifouling paints on boats below 25 m in length, new terms have been introduced in the 'small boat' market. Replacement products are generally based on copper metal oxides and organic biocides. Several studies have demonstrated the presence of these biocides in European ports and marinas of Spain, France, Germany and the United Kingdom. An extended survey of the antifouling biocides chlorothalonil, dichlofluanid, irgarol 1051 and sea-nine 211 was carried out in Greek ports and marinas of high boating activities from October 1999 to September 2000. The sampling sites were: Piraeus, Elefsina, Thessaloniki, Patras, Chalkida, Igoumenitsa, and Preveza (Aktio). The extraction of these compounds from the seawater samples was performed off-line with C18 solid phase extraction (SPE) disks while the determination was carried out with gas chromatography coupled to electron capture (ECD), thermionic (FTD) and mass spectroscopy (MS) detectors. The concentration levels of biocides were higher during the period from April to October. This seasonal impact depends on the application time of antifouling paints and mimic trends in the seasonal distribution of biocides in other European sites.     

Analytical methods for the determination of 9 antifouling paint booster biocides in estuarine water samples

Analytical procedures for the determination of nine organic booster biocides which are currently licensed for use in marine antifouling paints, and are thought likely to occur at concentrations in the ng 1⁻¹ range in estuarine water samples, are reviewed. A robust multiresidue method for the determination of four compounds (chlorothalonil, dichlofluanid, diuron and Irgarol 1051) is suggested. A route for the development of a method for the analysis of zinc pyrithione is outlined, based on an extraction method and subsequent derivatisation prior to determination by HPLC with fluorescence detection. Methodology for Zineb, Kathon 5287, TCMS pyridine and TCMTB is less clearly defined.     

Potential disruptive effects of copper-based antifouling paints on the biodiversity of coastal macrofouling communities

Environmental Science and Pollution Research - The expanded use of copper(I)-based antifouling paints (AF) has increased copper leaching into coastal environments, requiring attention and...     

Surface-sediment and hermit-crab contamination by butyltins in southeastern Atlantic estuaries after ban of TBT-based antifouling paints

Butyltin (BT) contamination was evaluated in hermit crabs from 25 estuaries and in sediments from 13 of these estuaries along about 2,000 km of the Brazilian coast. BT contamination in hermit crabs ranged from 2.22 to 1,746 ng Sn g^-1 of DBT and 1.32 to 318 ng Sn g^-1 of TBT. In sediment samples, the concentration also varied widely, from 25 to 1,304 ng Sn g^-1 of MBT, from 7 to 158 ng Sn g^-1 of DBT, and from 8 to 565 ng Sn g^-1 of TBT. BTs are still being found in surface sediments and biota of the estuaries after the international and Brazilian bans, showing heterogeneous distribution among and within estuaries. Although hermit crabs were previously tested as an indicator of recent BT contamination, the results indicate the presence of contamination, probably from resuspension of BTs from deeper water of the estuary.

Assessment of the risk posed by the antifouling booster biocides Irgarol 1051 and diuron to freshwater macrophytes

Antifouling paints are used to reduce the attachment of living organisms to the submerged surfaces of ships, boats and aquatic structures, usually by the release of a biocide. Two 'booster' biocides in common use are the triazine herbicide Irgarol 1051 (N-2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), and diuron (1-(3,4-dichlorophenyl)-3,3-dimethylurea), which are designed to inhibit algal photosynthesis. Previous research has been directed at the effects of these compounds in marine and estuarine environments. In 2001 we sampled the main rivers and shallow freshwater lakes (Broads) of East Anglia UK for Irgarol 1051, its metabolite GS26575 (2-methylamino-4-tert-butylamino-6-amino-s-triazine) and diuron in order to establish the baseline environmental concentrations of these compounds in freshwater systems of eastern UK and to investigate their possible effects on aquatic plants. Irgarol 1051, GS26575 and diuron were found in water samples collected from 21 locations. The highest concentrations were found in the Norfolk and Suffolk Broads in May. The rivers Great Ouse, Wissey, Bure and Yare also contained all three compounds, as did the Great Ouse Cut-off Channel. The toxicity of these biocides to three macrophyte species (Apium nodiflorum, Chara vulgaris, and Myriophyllum spicatum) was investigated. Deleterious effects on relative growth rate, the maximum quantum efficiency (Fv/Fm) of photosystem II and, for Apium, root mass production were found. C. vulgaris was generally most sensitive; growth, especially of roots, was strongly affected in A. nodiflorum; growth rate of M. spicatum was sensitive to diuron. No observed effect concentrations (NOEC) were interpolated using standard toxicological analysis. These were compared with measured environmental concentrations (MEC) to determine the ranges of risk quotients (MEC/NOEC). Both Irgarol 1051 and diuron represented significant risks to A. nodiflorum and C. vulgaris in this area.     

Natural radionuclides distribution and environmental impacts of ferruginous sand-siltstone (raw material) and their manufactured Ahmer oxide used as wall paints

Commercially known Ahmer oxide paints are prepared from raw material mainly composed of red iron oxides (hematite) and iron oxyhydroxides. The raw material used in manufacturing of Ahmer oxide comes from some localities in southwest Sinai such as Abu Thor, Allouga, and El lehian. The adsorption of uranium and other radioelements on iron oxides could make the raw material (red iron oxides) and their products environmentally hazardous. The studied samples were subjected to radiometric analysis using NaI (Tl) gamma-ray spectrometer. The average activity concentration of U, Th, Ra, and K are 108.7, 458.8, 88.8, and 627.5?Bq?kg^?1, respectively in raw material and 136.4, 14.6, 58.3, and 95.9?Bq?kg^?1 in Ahmer oxide. High values of activity concentrations of ²³⁸U, ²²⁶Ra, and ⁴⁰K were recorded in Allouga and El lehian raw material. High radioactivities of Allouga and El lehian raw material are mainly attributed to the presence of torbernite, zircon, and monazite, in addition to adsorbed elemental uranium in Ahmer oxide. absorbed dose rate (D), annual effective dose equivalent, radium equivalent activity (Ra_eq), external hazard index (H_ex), and internal hazard index (H_in), as well as representative gamma index (Iγ) were determined from the activity concentrations of ²²⁶Ra, ²³²Th, and ⁴⁰K. Some of the studied samples do not satisfy the universal standards.     

Comparative environmental impacts of glyphosate and conventional herbicides when used with glyphosate-tolerant and non-tolerant crops

The introduction of glyphosate-tolerant (GT) crops is expected to mitigate the environmental contamination by herbicides because glyphosate is less persistent and toxic than the herbicides used on non-GT crops. Here, we compared the environmental balances of herbicide applications for both crop types in three French field trials. The dynamic of herbicides and their metabolites in soil, groundwater and air was simulated with PRZM model and compared to field measurements. The associated impacts were aggregated with toxicity potentials calculated with the fate and exposure model USES for several environmental endpoints. The impacts of GT systems were lower than those of non-GT systems, but the accumulation in soils of one glyphosate metabolite (aminomethylphosphonic acid) questions the sustainability of GT systems. The magnitude of the impacts depends on the rates and frequency of glyphosate application being highest for GT maize monoculture and lowest for combination of GT oilseed rape and non-GT sugarbeet crops.     

Incorporating bioavailability into management limits for copper in sediments contaminated by antifouling paint used in aquaculture

Although now well embedded within many risk-based sediment quality guideline (SQG) frameworks, contaminant bioavailability is still often overlooked in assessment and management of contaminated sediments. To optimise management limits for metal contaminated sediments, we assess the appropriateness of a range methods for modifying SQGs based on bioavailability considerations. The impairment of reproduction of the amphipod, Melita plumulosa, and harpacticoid copepod, Nitocra spinipes, was assessed for sediments contaminated with copper from antifouling paint, located below aquaculture cages. The measurement of dilute acid-extractable copper (AE-Cu) was found to provide the most useful means for monitoring the risks posed by sediment copper and setting management limits. Acid-volatile sulfide was found to be ineffective as a SQG-modifying factor as these organisms live mostly at the more oxidised sediment water interface. SQGs normalised to %-silt/organic carbon were effective, but the benefits gained were too small to justify this approach. The effectiveness of SQGs based on AE-Cu was attributed to a small portion of the total copper being present in potentially bioavailable forms (typically <10% of the total). Much of the non-bioavailable form of copper was likely present as paint flakes in the form of copper (I) oxide, the active ingredient of the antifoulant formulation. While the concentrations of paint-associated copper are very high in some sediments, as the transformation of this form of copper to AE-Cu appears slow, monitoring and management limits should assess the more bioavailable AE-Cu forms, and further efforts be made to limit the release of paint particles into the environment.     

Risk assessment of environmental chemicals

This article is a summary from eleven important symposia. In these meetings, critical facts were discussed which are the necessary basis for the important legislation about toxic substances in Europe, in the U.S.A. and in Japan. This review article should also be of some help to the readers of “Chemosphere” for direct contacts with the experts mentioned. It is therefore an informative and coordinative survey, in which chemical and ecotoxicological details are largely omited.     

A new simple method with high precision for determining the toxicity of antifouling paints on brine shrimp larvae (Artemia): first results

The use of antifouling paints is the only truly effective method for the protection of underwater structures from the development of fouling organisms. In the present study, the surface to volume concept constitutes the basis for the development of a new and improved method for determining the toxicity of antifouling paints on marine organisms. Particular emphasis is placed on the attainment of a standardized uniformity of coated surfaces. Failure to control the thickness of the coat of paint in previous studies of this type, has led to inaccurate evaluation of the relative toxicity of samples. Herein, an attempt is made to solve this problem using a simple technique which gives completely uniform and smooth surfaces. The effectiveness of this technique is assessed through two series of experiments using two different types of test containers: 50 ml modified syringes and 7 ml multiwells. The results of the toxicity experiments follow a normal distribution around the average value which allows to consider these values as reliable for comparison of the level of toxic effect detected with the two types of test containers. The mean lethal concentration L(S/V)(50) in the test series conducted in the multiwells (20.38 mm(2)ml(-1)) does not differ significantly from that obtained in the test series using modified syringes (20.065 mm(2)ml(-1)). It can thus be concluded from this preliminary study that the new method and the two different ways of exposing the test organisms to the antifouling paints and their leachates gave reliable and replicable results.     

The logistics of public participation in environmental assessment

This paper starts by investigating the rationales for public participation in environmental assessment. It is contended that access to participation may refer both to means as well as ends; thus, some advocates of citizen participation favour involvement for social and or political reasons (i.e. the participation is the end in itself). However, the value of that participation may also, as we shall see, advance quality and depth of knowledge (i.e. the participation is viewed only as a means to an end). The initial two sections, therefore, paint two broad brushstrokes: the first concerns why we should require public participation, and the second why that participation may improve the quality of our environmental assessment procedure. Further, it is then argued that the issues and problems of public participation vary across different environmental issues and also vary across different stages of the environmental assessment procedure and according to the scientific disciplines and practices involved. This paper points the way towards an open and representative style in which communities are included in environment assessment processes as a source of new or better knowledge, as well as a contribution towards what the EU refers to as the 'horizontal participatory approach'. The paper briefly considers methodological issues concerning ways in which participation might be carried out.     

中国交通规划战略环境评价的若干问题探讨

《中华人民共和国环境影响评价法》实施5年多以来,交通规划战略环境评价的开展有效推进了中国交通建设的可持续发展。目前,该领域在理论研究和实践应用方面都取得了一定的成绩,但也存在一些不足。在回顾国内外交通规划战略环境评价发展历程和特点的基础上,就中国交通规划战略环境评价在层次性、定性与定量评价的把握以及如何有效融入决策过程等方面的问题进行了初步探讨,并建议尽早开展利益相关方分析、推广综合情景+定量模型的技术方法、引入制度分析方法并开展广泛的公众参与等,为完善中国的交通规划战略环境评价提供参考。     

规划环境影响评价探讨

以《中华人民共和国环境影响评价法》为依据 ,对实施规划环境影响评价的意义进行了分析 ,并提出了规划环境影响评价应遵循的原则、方法和基本程序     

Developing principles of good practice in integrated environmental assessment

In integrated environmental assessment, unlike many other fields of quantitative social and environmental science, there is a keen awareness of the need for quality and assurance, and principles of good practice. This paper explores what is involved in developing and maintaining good practice. The problems of quality assurance in such a field, apparently scientific but in practice something else, must be confronted. The existing approaches to effective practice are scrutinized the pitfalls of the quantitative path, the perils of GIGO with computers, and the hazards of modelling. The struggles of modellers with uncertainty are chronicled, first by recalling the IIASA energy study, and then reviewing J. van der Sluijs's research. The spectre haunting all these mathematical socio-environmental sciences is 'immaturity'; this is explored, and analogies are drawn with the design disciplines and history. Finally, the insights of 'Post-Normal Science' are applied, with the distinction between research and professional practice, the qualitative analysis of quantitative information, and the usefulness of the pedigree category in characterising nformation quality. The Post-Normal approach is discussed as a possible way forward from the insoluble problems of achieving good practice, and maintaining quality, in the field when it is conceived in purely quantitative terms.     

Enantioselectivity in environmental risk assessment of modern chiral pesticides

Chiral pesticides comprise a new and important class of environmental pollutants nowadays. With the development of industry, more and more chiral pesticides will be introduced into the market. But their enantioselective ecotoxicology is not clear. Currently used synthetic pyrethroids, organophosphates, acylanilides, phenoxypropanoic acids and imidazolinones often behave enantioselectively in agriculture use and they always pose unpredictable enantioselective ecological risks on non-target organisms or human. It is necessary to explore the enantioselective toxicology and ecological fate of these chiral pesticides in environmental risk assessment. The enantioselective toxicology and the fate of these currently widely used pesticides have been discussed in this review article.     

香港区域发展策略性环境影响评价的实践探讨

香港区域发展的策略性环境影响评价(简称环评)从20世纪80年代起步,已形成包括行政规定和法例规定的制度框架,其策略性环评的实践范围也逐步从规划、计划向政策、策略扩展.从评价过程、评价方法、公众参与时段安排、决策出发点等方面分析了2个香港区域发展的策略性环评案例.结果表明,为使策略性环评取得预想的成果并有助于可持续发展,...