Britta Eklund

Comparison of toxicity and release rates of Cu and Zn from anti-fouling paints leached in natural and artificial brackish seawater

Biocide-containing anti-fouling paints are regulated and approved according to the added active ingredients, such as Cu. Biocide-free paints are considered to be less environmentally damaging and do not need an approval. Zn, a common ingredient in paints with the potential of causing adverse effects has received only minor attention. Laboratory experiments were conducted in artificial brackish seawater (ASW) and natural brackish seawater (NSW) to quantify release rates of Cu and Zn from biocide-containing and biocide-free labeled eroding anti-fouling paints used on commercial vessels as well as leisure boats. In addition, organisms from three trophic levels, the crustacean Nitocra spinipes, the macroalga Ceramium tenuicorne and the bacteria Vibrio fischeri, were exposed to Cu and Zn to determine the toxicity of these metals. The release rate of Cu in NSW was higher from the paints for professional use (3.2-3.6 microg cm(-)(2)d(-1)) than from the biocide leaching leisure boat paint (1.1 microg cm(-)(2)d(-1)). Biocide-free paints did leach considerably more Zn (4.4-8.2 microg cm(-)(2)d(-1)) than biocide-containing leisure boat paint (3.0 microg cm(-)(2)d(-1)) and ship paints (0.7-2.0 microg cm(-)(2)d(-1)). In ASW the release rates of both metals were notably higher than in NSW for most tested paints. The macroalga was the most sensitive species to both Cu (EC(50)=6.4 microg l(-1)) and Zn (EC(50)=25 microg l(-1)) compared to the crustacean (Cu, LC(50)=2000 microg l(-1) Zn, LC(50)=890 microg l(-1)), and the bacteria (Cu, EC(50)=800 microg l(-1) and Zn, EC(50)=2000 microg l(-1)). The results suggest that the amounts of Zn and Cu leached from anti-fouling paints may attain toxic concentrations in areas with high boat density. To fully account for potential ecological risk associated with anti-fouling paints, Zn as well as active ingredients should be considered in the regulatory process.

Review on toxicity testing with marine macroalgae and the need for method standardization––exemplified with copper and phenol

Toxic effects on macroalgae have been compiled. Eighty-two articles have been found in literature during 1959-2000. A total of 120 substances were investigated using 65 different macroalgae species. About one-third of the tested compounds were organic substances (33%), another third metal-organic substances (35%), and the last third were oils (14%), metals (8%), detergents (7.5%) and other inorganic chemicals (2.5%). Half of the substances were only tested once on a single species. Likewise, toxicity data has only been reported for one chemical tested on a single occasion for about half of the 65 species. Thus little is known about the toxic effects on marine macroalgae. The objectives of the previous studies undertaken varied and therefore the toxicity data was presented in numerous ways, e.g. using different exposure times, temperature, light intensity, light regime, salinity, and nutrients, which makes a direct comparison of the data difficult. This review also shows that many stages in the lifecycle of macroalgae are often more sensitive to toxic substances than other aquatic organisms. Consequently, tests using macroalgae may discover toxicity earlier, which would in turn also protect the fauna. If toxic compounds have a negative affect on the distribution and growth of structurally and functionally dominating macroalgae, there may indirectly be a large and harmful influence on the whole marine coastal ecosystem. For this reason tests on macroalgae should be included in control programs along the coasts.

Toxicity of anti-fouling paints for use on ships and leisure boats to non-target organisms representing three trophic levels

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 per thousand 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.

Food quality effects on copepod growth and development: implications for bioassays in ecotoxicological testing.

We evaluated effects of six algal species in 25 combinations on growth and reproduction of the harpacticoid copepod Nitocra spinipes. In the first lifecycle test, Rhodomonas salina, Phaeodactylum tricornutum, and Dunaliella tertiolecta were used. The results showed that R. salina was the best food, whereas P. tricornutum (0% development success) and D. tertiolecta (41.7% malformations) were poor food items. In the second lifecycle test, a mixture of R. salina, Tetraselmis suecica, and Thalassiosira weisflogii (selected from screening tests) was tested together with a mono-diet of R. salina. Also in this test, copepods fed R. salina performed better (i.e. had higher survival and reproductive success) compared with the other treatment. We conclude that R. salina is appropriate to use as food in toxicity testing with N. spinipes, whereas some of the algae commonly used as feed in ecotoxicological tests with other copepods had detrimental effects on the development, reproduction, and survival of N. spinipes.

Characterization of additional sewage treatment technologies : Ecotoxicological effects and levels of selected pharmaceuticals, hormones and endocrine disruptors

In the present study, two conventional (with and without sand filter) and four additional (moving bed biofilm reactor, ozone, moving bed biofilm reactor combined with ozone and a membrane bio reactor) treatment technologies were operated in small-scale at Hammarby Sjöstad sewage treatment plant, Stockholm, Sweden. The effluents were tested with five short-term (≤ 7 days exposure) ecotoxicological tests, and analyzed for a number of target analytes, comprising pharmaceuticals, natural hormones and industrial chemicals. Overall, the tested effluents generated few adverse effects at lower concentrations (< 50% sewage effluent), and no major differences were observed between any of the treatments. The effluent treated with the moving bed biofilm reactor resulted in the lowest effects in the ecotoxicological tests. The most efficient treatment technology with regard to the pharmaceutical residues was the ozone treatment, which however caused negative effects in some of the ecotoxicological tests.

Two new growth inhibition tests with the filamentous algae Ceramium strictum and C. tenuicorne (Rhodophyta)

Two growth inhibition tests using the red marine macroalgae Ceramium strictum and the brackish water relative C. tenuicorne have been developed. Besides using phenol as a reference substance, the toxicity of a metal, a flame retardant and a complex effluent water were assayed. The two methods are reliable and repeatable bioassays for salinities between 4 and 30 per thousandth. The coefficients of variation (CV) for toxicity of the reference substance phenol were 15% for the Stereo Microscope Analysis test and between 24 and 51% for the Computer Image Analysis test (n=5). Ceramium spp. are common and important primary producers in temperate coastal waters and are thus relevant as test organisms. Both algae grow well in laboratorial conditions and tests can be performed all year around.

Effect of Organic Complexation on Copper Accumulation and Toxicity to the Estuarine Red Macroalga Ceramium tenuicorne : A Test of the Free Ion Activity Model

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.

Influence of salinity and organic matter on the toxicity of Cu to a brackish water and marine clone of the red macroalga Ceramium tenuicorne

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.

New analytical application for metal determination in antifouling paints

Despite the ban of applying TBT coatings on leisure boats in the late 80s, recent studies show an ongoing spread of TBT from leisure boats, particularly during hull cleaning events. Therefore, countries in EU have adopted expensive measures to clean this wash water. A more cost-efficient measure is to focus directly on the source, i.e. identify leisure boats with high concentrations of TBT and prescribe boat owners to remove the paint. We have developed a new antifouling paint application for a handheld X-ray fluorescence (XRF) analyzer to be used for identifying boats with high area concentrations (µg/cm(2)) of Sn (indication that the hull contains TBT paint residues). Copper and zinc are also included in the application since these metals are used in the vast majority of todays paints. A blind test with up to four layers of TBT-, copper- and zinc-based paints showed good correlation between XRF-measured area concentrations and chemically analyzed concentrations. Future usage of the applications involves identification of boat hulls in particular with high Sn concentrations and also with high Cu and Zn concentrations. This method has the potential to become a useful tool in regulatory management of existence and use of toxic elements on boat hulls.

A 7-day reproduction test with the marine red alga Ceramium strictum

Abstract A sensitive short-term toxicity test using a marine red macroalga has been developed. It is a static-renewal test using the gametophytes of Ceramium strictum (Harv.). Sexually mature male and female branches are exposed for 24 h to the test substance. The test parameter is the number of cystocarps formed in different concentrations of the test substance compared to the control. After the exposure follows a 6-day recovery period where the cystocarps develop to a size that can be detected in a stereo microscope. The test has many advantages, such as: the gametophytes are constantly fertile, small volumes of each test concentrations are sufficient to perform the test with a large number of plants, the test parameter (cystocarps) is easy recognizable, the results can be read any time between days 7 and 10 after the start of the test and the time needed to carry out the test as well as to keep the stock cultures is short.