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Organisationseinheit der BAM
Treated wood is frequently used for construction. However, there is a need to ensure that biocides used for the treatment are not a threat for people or environment. The paper focused on Pinus sylvestris treated with copper–boron–azole (CBA), containing tebuconazole as organic biocide and monoethanolamine (Mea).
This study investigates chemical mechanisms of fixation and mobilisation involved in the leaching process of the used inorganic and organic biocides in CBA.
A pH dependent leaching test was performed, followed by a set of complementary analysis methods in order to identify and quantify the species released from wood. The main findings of this study are:
-Organic compounds are released from untreated and treated wood; the quantity of released total organic carbon, carboxylic and phenolic functions increasing with the pH.
-Nitrogen containing compounds, i.e. mainly Mea and its reaction products with extractives, are released in important quantities from CBA treated wood, especially at low pH.
-The release of copper is the result of competitive reactions: fixation via complexation reactions and complexation with extractives in the liquid phase. The specific pH dependency of Cu leaching is explained by the competition of ligands for protonation and complexation.
-Tebuconazole is released to a lesser extent relative to its initial content. Its fixation on solid wood structure seems to be influenced by pH, suggesting interactions with –OH groups on wood. Boron release appears to be pH independent and very high. This confirms its weak fixation on wood and also no or weak interaction with the extractives.
Leaching of biocides from construction products is currently a research topic receiving attention from the European regulation authorities (CEN/TC 351).
In this paper we have focused on the leaching behaviour of CBA (copper-borateazoles) treated Pinus sylvestris.
To better define the chemistry of the leaching phenomena, two leaching tests (a static equilibrium test and a dynamic surface leaching test) have been carried out on untreated and treated wood, which offered more information about how the leaching of biocides interferes with other substances released from the wood structure.
Eluates, in liquid and lyophilised form, were further analyzed by analytical methods.
Organic (tebuconazole) and inorganic (Cu, B) biocides were quantified and several organic compounds have been identified (e.g.
carboxylic acids, phenols, amines, etc.).
Also, the total amount of phenols and of carboxylic groups was determined.
Results on inorganic compounds are in accordance with previous studies made on treated wood.
Furthermore, organic carbon, tebuconazole and other organic compounds' behaviour was extensively investigated.
This study aims to complete existing leaching data and to help developing a chemical model for several biocides in wood, including Cu, B and tebuconazole.
Stormwater from urban areas can transport biocidally active substances and related transformation products from buildings into the environment. The occurrence of these substances in urban runoff depends on the availability of water, and on ultraviolet radiation exposure that causes photolytic reactions. In a systematic laboratory study, painted test specimens were exposed to either ultraviolet radiation, water contact, or a combination of both. Leaching of the biocidally active substances carbendazim, diuron, octylisothiazolinone, terbutryn, and selected transformation products of terbutryn and diuron were observed under various exposure conditions. Remaining concentrations of these substances in the paint were quantified. It was demonstrated that the distribution of active substances and transformation products in eluates and in the coatings themselves differs with exposure conditions. Strategies for environmental monitoring of biocide emissions need to consider the most relevant transformation products. However, environmental concentrations of biocidally active substances and transformation products depend on earlier exposure conditions. As a consequence, monitoring data cannot describe emission processes and predict expected leaching of biocidally active substances from buildings if the data are collected only occasionally.
Biocide leaching was investigated for acrylate and vinyl acetate based coatings containing biocides either as liquid formulations or microcapsules. Laboratory and field tests indicate similar relations of results on carbendazim, diuron, terbutryn and OIT from different coatings in laboratory and field experiments. Emissions were higher in EN 16105 laboratory tests than from vertically installed test specimens exposed to weathering, and slower for microencapsulated biocides. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. Emission curves related to runoff water were similar in repeated field experiments. Relative humidity, temperature and global radiation were identified as meteorological factors that affect leaching by complex interaction besides the amount of driving rain.
Biocide leaching was investigated for acrylate and vinyl acetate based coatings containing biocides either as liquid formulations or microcapsules. Laboratory and field tests indicate similar relations of results on carbendazim, diuron, terbutryn and OIT from different coatings in laboratory and field experiments. Emissions were higher in EN 16105 laboratory tests than from vertically installed test specimens exposed to weathering, and slower for microencapsulated biocides. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. Emission curves related to runoff water were similar in repeated field experiments. Relative humidity, temperature and global radiation were identified as meteorological factors that affect leaching by complex interaction besides the amount of driving rain.
This report supports the implementation of European regulations on biocidal products for the product types 7, 9 and 10. Emission of active substances from material preservatives into environmental compartments can occur due precipitation. Risk characterisations have to be based on estimations of environmental concentrations of target substances leached from material preservatives. Harmonised test procedures are required to predict environmental impact due to leaching. Seventeen treated articles, mainly paints, but also a textile, sealing tapes and sealing masses were investigated by intermittent contact to water to prove suitability of the proposed laboratory test procedure. Parameters that affect leaching of active substances were examined.
Further development of a semi-analytical model to describe laboratory leaching data revealed that the model can be improved if changes of the leachability of substances during the test are supposed and integrated. Six paints and a textile were exposed to weathering to compare results from laboratory and field experiments. Similarities between leaching processes in both test approaches were observed. Generally, emissions of active substances are considerably higher in laboratory tests than from vertically installed test specimens exposed to weathering. Competing processes that cause losses of active substances can occur in both tests, but to a higher degree in field experiments. In addition, the influence of meteorological parameters on leaching processes was investigated. Factors besides the amount of driving rain were identified that effect leaching processes by complex interaction. Relations between laboratory and field data were analysed, and the applicability of the semi-analytical model was tested for field data. Guidance documents for leaching tests under laboratory and field conditions were drafted and discussed with experts on EU Level workshop 3./4. July 2014, BAM, Berlin), and are included in this Report.
Background: Biocidal products can be sources of active substances in surface waters caused by weathering of treated articles. Marketing and use of biocidal products can be limited according to the European Biocidal Products Regulation if unacceptable risks to the environment are expected. Leaching of active substances from treated articles was observed in field experiments to obtain information on leaching processes and investigate the suitability of a proposed test method.
Results: Leaching under weathering conditions proceeds discontinuously and tends to decrease with duration of exposure. It mainly depends on the availability of water, but is also controlled by transport processes within the materials and stability of the observed substances. Runoff amount proved to be a suitable basis to compare results from different experiments. Concentrations of substances are higher in runoff collected from vertical surfaces compared to horizontal ones, whereas the leached amounts per surface area are higher from horizontal surfaces. Gaps in mass balances indicate that additional processes such as degradation and evaporation may be relevant to the fate of active substances in treated articles. Leached amounts of substances were considerably higher when the materials were exposed to intermittent water contact under laboratory conditions as compared to weathering of vertically exposed surfaces.
Conclusions: Experiences from the field experiments were used to define parameters of a procedure that is now provided to fulfil requirements of the Biocidal Products Regulation. The experiments confirmed that the amount of water which is in contact with exposed surfaces is the crucial parameter determining leaching of substances.