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Release rates and toxicity of metals from anti-fouling paints and the role of chemical speciation
Stockholm University, Faculty of Science, Department of Applied Environmental Science (ITM).
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The aim of this doctoral thesis was to investigate and improve the risk assessment of anti-fouling paints. A new method, the Petri-dish method, was developed to determine release rates of copper and zinc from anti-fouling paints (Paper I). The release rates of zinc were substantially higher from the biocide-free leisure boat paints than from the biocide-leaching paints. In Paper II, the potential toxicity of paint leachates was assessed and the biocide-free paint proved to be the most toxic paint investigated. Zinc, a supposedly non-biocidal ingredient in copper-based and other antifouling paints, was found to contribute significantly to the observed toxicity of all leisure boat paints investigated. This means that risk assessment of an anti-fouling paint based on only the active biocidal ingredient in the formula is insufficient. A more holistic approach, based on hazard identification and dose-response assessment of anti-fouling paint leachate, with all ingredients taken into consideration, is recommended. This can be achieved by the Petri-dish method, which combines chemical analysis with ecotoxicological tests of paint leachates. In Paper III and IV, the effects of salinity and organic matter on copper bioaccumulation and toxicity to the red macroalga Ceramium tenuicorne were studied. Salinity had only a minor effect in ameliorating copper toxicity, whereas the organic matter concentration had a significant effect in reducing the bioavailability and hence copper toxicity at all salinities tested. Copper uptake and bioaccumulation by C. tenuicorne showed that the macroalga could access a sizeable fraction of organically-complexed copper in addition to Cu2+, when Cu2+ concentration to the cell membrane is diffusion limited. This observation implies that the setting of environmental quality standards (EQSs) for copper and other metals through the Biotic Ligand Model (BLM) is inappropriate in predicting copper uptake and hence toxicity to C. tenuicorne.

Place, publisher, year, edition, pages
Stockholm: Department of Applied Environmental Science (ITM), Stockholm University , 2011. , 37 p.
Keyword [en]
Anti-fouling paints, Toxicity test, Ceramium tenuicorne, Nitocra spinipes, Copper, Zinc, Free Ion Activity Model (FIAM)
National Category
Natural Sciences
Research subject
Applied Environmental Science
Identifiers
URN: urn:nbn:se:su:diva-61992ISBN: 978-91-7447-352-2 OAI: oai:DiVA.org:su-61992DiVA: diva2:439679
Public defence
2011-10-21, William-Olssonsalen, Geovetenskapens hus, Svante Arrhenius väg 14, Stockholm, 09:30 (Swedish)
Opponent
Supervisors
Available from: 2011-09-29 Created: 2011-09-06 Last updated: 2011-09-19Bibliographically approved
List of papers
1. Comparison of toxicity and release rates of Cu and Zn from anti-fouling paints leached in natural and artificial brackish seawater
Open this publication in new window or tab >>Comparison of toxicity and release rates of Cu and Zn from anti-fouling paints leached in natural and artificial brackish seawater
2010 (English)In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 408, no 12, 2459-2466 p.Article in journal (Refereed) Published
Abstract [en]

Quantification of release rates of Cu and Zn from biocide-containing and biocide-free antifouling paints, used on ships and leisure boats, were conducted in brackish artificial and natural seawater (ASW and NSW). To determine the toxicity of Cu and Zn, toxicity tests were performed with organisms from three trophic levels. Generally, the release rates of both Cu and Zn were higher in ASW than in NSW for the tested paints. The release rate of Cu in NSW was higher from the ship paints (3.2–3.6 μg cm-2d-1) than from the leisure boat paint (1.1 μg cm-2d-1). Biocide-free paints leached more Zn (4.4–8.2 μg cm-2d-1) than the biocide-containing paints (0.7–3.0 μg cm-2d-1). In conclusion, both Cu and Zn may be toxic to non-target organisms in areas with high boat density. To account for ecological risk associated with anti-fouling paints, Zn as wells as the active ingredients should be considered.

Place, publisher, year, edition, pages
Elsevier B.V., 2010
Keyword
Baltic Sea; Macroalga; Crustacean; Ceramium; Nitocra
National Category
Ecology
Identifiers
urn:nbn:se:su:diva-29639 (URN)10.1016/j.scitotenv.2010.02.036 (DOI)
Note
3Available from: 2009-09-09 Created: 2009-09-09 Last updated: 2017-12-13Bibliographically approved
2. Toxicity of anti-fouling paints for use on ships and leisure boats to non-target organisms representing three trophic levels
Open this publication in new window or tab >>Toxicity of anti-fouling paints for use on ships and leisure boats to non-target organisms representing three trophic levels
2010 (English)In: Environmental Pollution, ISSN 0269-7491, E-ISSN 1873-6424, Vol. 158, no 3, 681-687 p.Article in journal (Refereed) Published
Abstract [en]

Leachates of anti-fouling paints for use on ships and leisure boats are examined for their ecotoxicological potential. Paint leachates were produced in both 7‰ artificial (ASW) and natural seawater (NSW) and tested on three organisms, the bacterium Vibrio fischeri, the macroalga Ceramium tenuicorne, and the crustacean Nitocra spinipes. Generally, leaching in ASW produced a more toxic leachate and was up to 12 times more toxic to the organisms than was the corresponding NSW leachate. The toxicity could be explained by elevated concentrations of Cu and Zn in the ASW leachates. Of the NSW leachates, those from the ship paints were more toxic than those from leisure boat paints. The most toxic paint was the biocide-free leisure boat paint Micron Eco. This implies that substances other than added active agents (biocides) were responsible for the observed toxicity, which would not have been discovered without the use of biological tests.

Place, publisher, year, edition, pages
Elsevier B.V, 2010
Keyword
Baltic Sea; Macroalga; Crustacean; Ceramium; Nitocra
National Category
Biological Sciences
Identifiers
urn:nbn:se:su:diva-29640 (URN)10.1016/j.envpol.2009.10.024 (DOI)000275002900006 ()
Available from: 2009-09-09 Created: 2009-09-09 Last updated: 2017-12-13Bibliographically approved
3. Influence of salinity and organic matter on the toxicity of Cu to a brackish water and marine clone of the red macroalga Ceramium tenuicorne
Open this publication in new window or tab >>Influence of salinity and organic matter on the toxicity of Cu to a brackish water and marine clone of the red macroalga Ceramium tenuicorne
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2011 (English)In: Ecotoxicology and Environmental Safety, ISSN 0147-6513, E-ISSN 1090-2414, Vol. 74, no 4, 636-642 p.Article in journal (Refereed) Published
Abstract [en]

Cu is a major active component in anti-fouling paints, which may reach toxic levels in areas with intense boat traffic and therefore is a metal of environmental concern. The bioavailability of metals is influenced by factors such as salinity and organic matter measured as total organic carbon (TOC). The influence of these two factors was studied, with a focus on brackish water conditions, by exposing a marine and a brackish water clone of the red macroalga Ceramium tenuicorne to Cu in different combinations of artificial seawater (salinity 5–15‰) and TOC (0–4 mg/L) in the form of fulvic acid (FA). In addition, the toxicity of Cu to both clones was compared in salinity 10‰ and 15‰. The results show that by increasing TOC from 0 to 2 and 4 mg/L, Cu was in general less toxic to both algal clones at all salinities tested (p<0.05). The effect of salinity on Cu toxicity was not as apparent, both a positive and negative effect was observed. The brackish water clone showed generally to be more sensitive to Cu in salinity 10‰ and 15‰ than the marine counterpart. In conclusion, FA reduced the Cu toxicity overall. The Cu tolerance of both strains at different salinities may reflect their origin and their adaptations to marine and brackish water.

Keyword
Copper, Fulvic acid, DOC, Macroalgae, Ceramium tenuicorne, Ecotoxicology, Effect concentration
National Category
Earth and Related Environmental Sciences
Identifiers
urn:nbn:se:su:diva-61987 (URN)10.1016/j.ecoenv.2010.09.013 (DOI)000290553400012 ()
Available from: 2011-09-06 Created: 2011-09-06 Last updated: 2017-12-08Bibliographically approved
4. Effect of Organic Complexation on Copper Accumulation and Toxicity to the Estuarine Red Macroalga Ceramium tenuicorne: A Test of the Free Ion Activity Model
Open this publication in new window or tab >>Effect of Organic Complexation on Copper Accumulation and Toxicity to the Estuarine Red Macroalga Ceramium tenuicorne: A Test of the Free Ion Activity Model
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2011 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 45, no 7, 3145-3153 p.Article in journal (Refereed) Published
Abstract [en]

Current water quality criteria (WQC) regulations on copper toxicity to biota are still based on total dissolved (<0.4 μm membrane filter) copper concentrations with a hardness modification for freshwaters. There are however ongoing efforts to incorporate metal speciation in WQC and toxicity regulations (such as the biotic ligand model-BLM) for copper and other metals. Here, we show that copper accumulation and growth inhibition of the Baltic macroalga Ceramium tenuicorne exposed to copper in artificial seawater at typical coastal and estuarine DOC concentrations (similar to 2−4 mg/L-C as fulvic acid) are better correlated to weakly complexed and total dissolved copper concentrations rather than the free copper concentration [Cu2+]. Our results using a combination of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) measurements and model calculations (using visual MINTEQ incorporating the Stockholm Humic Model) show that copper accumulation in C. tenuicorne only correlates linearly well to [Cu2+] at relatively high [Cu2+] and in the absence of fulvic acid. Thus the FIAM fails to describe copper accumulation in C. tenuicorne at copper and DOC concentrations typical of most marine waters. These results seem to indicate that at ambient total dissolved copper concentration in coastal and estuarine waters, C. tenuicorne might be able to access a sizable fraction of organically complexed copper when free copper concentration to the cell membrane is diffusion limited.

National Category
Earth and Related Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-61989 (URN)10.1021/es1039166 (DOI)000288841500094 ()
Available from: 2011-09-06 Created: 2011-09-06 Last updated: 2017-12-08Bibliographically approved

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