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Biological test, AAS and EPR study of copper monoethanolamine complex with quaternary ammonium compounds as a wood preservative
2003 - IRG/WP 03-30321
Experiments were carried out on the wood preservative with a strong fungicidal activity based on Cu(II) carbonate, 2-aminoethanol (monoethanolamine) and quaternary ammonium compound (QAC). The object of the performed investigations was sapwood of Scots pine (Pinus sylvestris L.) treated with Cu-EA-QAC formulation. Mycological investigations were carried out according to EN 113 and EN 84 standards. The retention of the copper ions in the wood grows nonlinearly with concentration (in %) of the impregnating solution from 0,25 kg/m3 at 0.03% to 1,55 kg/m3 at 0.21% (i.e. nearly 6 times) whereas the copper leachability decreases 2,5 times from 15% to 6% in the same range. These results indicate good fixation of the copper to the wood and high leaching resistance. EPR results and computer simulations of the observed EPR spectra shows that in Cu-EA aqueous solution the Cu(EA)2(H2O)2 complexes exist and the main coordination plane is not destroyed in impregnating solution and in the wood. In Cu-EA-QAC-BA solution the Cu(EA)2(QAC)2 complexes appear whereas EPR spectra of the treated wood indicate coexistence of a few types of Cu-complexes. We have identified strongly fixed Cu(EA)2O2 and Cu(EA)2O complexes with oxygens atoms from wood functional groups.
B Mazela, I Polus, S K Hoffmann, J Goslar

Distribution and availability of preservative components in ACQ treated wood - effects of coatings and weathering
2010 - IRG/WP 10-30537
Copper and quaternary ammonium compound (quat) distributions across lumber (gradients) and availability, as measured by amount removed by intensive leaching of wood flour, were measured in ACQ treated southern pine lumber. Samples were evaluated just after treatment and stabilization, or after 3 years of laboratory storage, or after 3 years of natural weathering exposure. The objective was to investigate how the distributions of copper, quat and monoethanolamine (MEA) changed under different exposure conditions to try to explain the long terms effects of semi-transparent wood coatings to reduce leaching, even after partial failure of the coatings. In unweathered lumber, there was a slight copper gradient from the surface to the interior of the lumber and a steeper quat gradient. Analysis of specimens after 3 years of weathering exposure confirmed the effectiveness of the coatings to reduce copper and quat leaching and showed that quat leaching from uncoated samples was substantial. There was little effect of aging indoors on availability of ACQ components. However, the availability of copper was significantly reduced after 3 years of natural exposure, even after accounting for the copper that leached during weathering. It was observed that the MEA availability was greatly reduced, presumably by preferential leaching compared to copper and quat during weathering. This appears to have reduced the amount of soluble/available copper resulting in lower long term copper leaching, especially in coated samples that were protected from high copper losses by the effect of the coating. The reduced quat leaching from coated samples is attributed to the long term effectiveness of the coatings in the earlywood portions of the samples.
T Ung, M Nejad, P Cooper

Effect of pretreatment of wood surfaces with a copper monoethanolamine solution on the natural weathering performance of semitransparent stains
2019 - IRG/WP 19-40881
Semitransparent stains for wood products are favored for outdoor applications in Japan because these finishes do not hide the wood grain. However, the photoprotective effects of wood surfaces are low, therefor there is a need to improve the weathering performance. We examined the natural weathering performance of semitransparent stains on wood pretreated with a copper monoethanolamine solution (CuA) to improve its photostability. Untreated and pretreated with CuA Japanese larch (Larix kaempferi), Todo fir (Abies sachalinensis), and Japanese cedar (Cryptomeria japonica) wood panels were finished with semitransparent stains containing a different type of resins and colours and exposed outdoors in Hokkaido, Japan for 24 months. Results from the visual assessment and statistical analysis using the Kaplan-Meier estimates of survival analysis showed that the formation of cracks predominantly observed and the stains performed better on pretreated than untreated panels. We conclude that the natural weathering performance of semitransparent stains can be enhanced by using CuA pretreatment. However, further studies would be needed to clarify the reason why the effectiveness of CuA pretreatment differ from resin type and/or wood species.
S Isaji, H Shibui, Y Hirabayashi

Preliminary study of the fungicidal and structural variability in copper naphthenates and naphthenic acids
1996 - IRG/WP 96-30114
Copper naphthenates, an oil-borne wood preservative listed by the American Wood-Preservers' Association (AWPA), is manufactured by complexing copper(II) with naphthenic acids. Prior to AWPA listing as a wood preservative, field experiments showed that copper naphthenates generally had good stability and were active against wood-destroying organisms. Recently, however, there have been reports of some copper naphthenate-treated poles rapidly failing. One possible explanation for the varying effectiveness could be that the structure, and resulting biological activity, of the naphthenic acids used to make copper naphthenate may vary. To test this hypothesis several naphthenic acids and copper naphenates were obtained and their fungicidal activity against three wood-destroying fungi measured. In addition, the chemical structure of the naphthenic acids were examined by proton- and carbon- NMR. Different activities were observed, especially against a copper-tolerant fungus. Some apparent correlations were seen between the fungicidal activity and chemical structures for the few samples studied.
T Schultz, D D Nicholas, L L Ingram Jr, T H Fisher

Sequestration of copper ions by the extracellular mucilaginous material (ECMM) of two wood rotting basidiomycetes
2004 - IRG/WP 04-10533
The radial growth rate of colonies originating from either whole or ECMM-free inocula of Coriolus versicolor was investigated. The presence of ECMM allowed colonies to maintain higher growth rates than those form ECMM-free inocula up to 2 mM CuSO4 in the medium. The ECMM of C. versicolor and G. trabeum was able to reduce the diffusion of copper ions in solution. The ‘raw’ ECMM of both fungi had a greater ability to reduce the diffusion of copper ions than ECMM which had been subject to dialysis to remove soluble, low molecular weight components. The ‘insoluble’ fraction of ECMM for both species was more effective than the ‘soluble’ fraction at reducing the diffusion of copper ions. It is concluded that ECMM confers some protection to hyphae against the toxic effects of copper ions on growth in vivo and that this due to the binding of copper ions to both the polysaccharide and to low molecular weight components of the ECMM
D Vesentini, D J Dickinson, R J Murphy

Influence of different fixation and ageing procedures on the leaching behaviour of copper from selected wood preservatives in laboratory trials
2003 - IRG/WP 03-20264
The paper focuses on the role of different parameters, such as fixation, sample size, wood species, and leaching in internationally standardized ageing procedures for wood preservatives from Europe, Japan and the United States. The leaching protocols used were EN 84, JIS K 1571 and AWPA E11 protocols. The wood species were Scots pine, Sugi and Southern Yellow Pine respectively. Three types of commercially important copper-based wood preservatives were used as model formulations, namely copper/copper-HDO, ammoniacal copper/quat and CCA. The most important factors determining the extent of copper leaching in the different lab trials were the sample size (volume/surface ratio) and the fixation conditions prior to leaching. On the other hand, the wood species and the leaching protocol itself were found to have only minor influence on the copper leaching rate in the test methods included in this study.
J Habicht, D Häntzschel, J Wittenzellner

International collaborative laboratory comparison of two wood preservatives against subterranean termites: Third update and first report
1996 - IRG/WP 96-10174
At the 24th annual meeting of IRG in Orlando, USA, in May 1993 an international subterranean termite laboratory bioassay to compare the various preferred termite protocols used by IRG termitologists was initiated. The author was nominated to co-ordinate this comparative laboratory evaluation of two wood preservatives, copper-chrome-arsenic (CCA) and copper naphthenate (Cu-Na) against the subterranean termites used as test termites in Australia, France, Japan, Thailand, United Kingdom and the Unites States of America. Solutions of these two wood preservatives were prepared and impregnated into Pinus radiata wood blocks to obtain loading of 0.0, 0.5, 1.0, 2.0 and 4.0 kg/m³ respectively. All preservative treatments were carried out at the Division of Forestry and Forest Products in Melbourne. The treated specimens were dispatched to the participating researchers who subjected these specimens to attack by their test termite species, and have now returned the specimens to Melbourne. This paper reports the amount of wood consumed and the mean mass loss (%) on both treated and untreated wood blocks by the termites in the various laboratory bioassays.
J R J French

Types of decay observed in CCA-treated pine posts in horticultural situations in New Zealand
1984 - IRG/WP 1226
The few reported failures of 11-12-year-old horticultural posts in New Zealand in 1982 were caused by brown-rot. A subsequent survey of CCA-treated posts in all the major horticultural areas has revealed decay of many posts. A microscopic examination of these posts has shown decay by brown-rot, white-rot, soft-rot and bacteria. Several types of bacterial decay have been observed.
J A Drysdale, M E Hedley

An investigation of the effects of pre-steaming on the treatment of sawn spruce timber with Celcure A, a copper-chrome-arsenic preservative
1981 - IRG/WP 3150
Difficulties in the treatment of spruce using standard vacuum/pressure techniques with both water-borne and organic solvent preservatives are well known. We have evaluated the influence of steaming on treatability with a waterborne CCA preservative.
C R Coggins

Electrodialytic remediation of creosote and CCA treated timber wastes
2002 - IRG/WP 02-50190
There is a growing concern about the environmental issue of impregnated timber waste management, since an increase in the amount of waste of treated wood is expected over the next decades. Presently, no well-documented treatment technique is yet available for this type of waste. Alternative options concerning the disposal of treated wood are becoming more attractive to study, especially the ones that may promote its re-use. Inside this approach, the electrodialytic process (ED) seems a promising technique for removal of preservative chemicals from treated wood waste. The method uses a direct electric current and its effects in the matrix as the “cleaning agent”, combining the electrokinetic movement (mainly due to electromigration, but also electro-osmosis and electrophoresis), with the principle of electrodialysis. This work reports results from the application of the electrodialytic process to an out-of-service Portuguese creosote and CCA-treated Pinus pinaster Ait. railway sleeper and pole. The behaviour of the process is described and the main results discussed. The average removal rate, estimated in accordance with prEN 12490, for creosote from treated timber waste was around 40 %.. For CCA treated timber waste, experimental conditions that could optimise the process efficiency (e.g. current density, time) were studied. The highest removal rates obtained until now, in our studies, were 93 % of Cu, 95 % of Cr and 99 % of As for sawdust using 2.5 % oxalic acid (w/w) as the assisting agent. For CCA treated wood waste in the form of chips, the best removal rates obtained until now were 84 % of Cu, 91 % of Cr and 97 % of As.
E P Mateus, A B Ribeiro, L Ottosen

Fungicidal activity of some organic solvents, copper carboxylates and their complexes with 2-aminoethanol
1997 - IRG/WP 97-30136
We evaluated the activity of eight organic solvents against wood - rotting fungus Trametes versicolor in order to choose the most appropriate one for rapid screening tests of some copper(II) carboxylates and their adducts with 2-aminoethanol. Their activity against the selected fungus was classified in the following order: chloroform > N,N-dimethylformamide > acetonitrile > methanol > dimethyl sulfoxide > ethanol > acetone. The non-polar white spirit did not dissolve in the growth medium and the results could not be directly compared with the results for other solvents. As an appropriate solvent for screening of the tested copper(II) carboxylates, dimethyl sulfoxide (DMSO) was chosen. Minimal inhibitory concentration against Trametes versicolor of the screened carboxylates was in the concentration range of 1x10-4 to 1x10-3 mol/l. Coordinated amine ligands slightly, and not significantly, decreased fungicidal properties of the tested carboxylates.
M Petric, F Pohleven

Termite resistance of pine wood treated with chromated copper arsenates
1997 - IRG/WP 97-30128
Two four-week, no-choice laboratory tests were performed with CCA-treated southern yellow pine and radiata pine against Formosan subterranean termites, Coptotermes formosanus. CCA retentions as low as 0.05 kg/m3 (0.03 pcf) provided protection from all but light termite attack (rating of 9 on a 10-point visual scale). Similar and consistent light attack on wafers containing retentions as high as 6.4 kg/m3 (0.4 pcf), coupled with complete termite mortality, demonstrates that the mode of action of CCA treatments relies upon toxicity rather than having any repellent effects against termites.
J K Grace

Problems of fixation of CCA-preservatives in palm-wood
1985 - IRG/WP 3338
Palm-wood may be used for posts and poles where it needs proper treatment for long time use. Based on observations by W. Killmann on low CCA-fixation in palm-wood, samples of Jubaea-palm grown in a Greenhouse at Hamburg, have been treated in two different series with a 4% solution of CCA-type B. After 1-16 weeks of storage the blocks were split into sticks of 1-2 mm² and leached. In all series 50% of the chromium and copper content of the individual blocks was leached independent of the time of storage, whereas simultaneously treated pinewood samples showed complete fixation after 4 weeks of storage.
H Willeitner, K Brandt

Field Testing of Copper Carboxylate Preservatives
2003 - IRG/WP 03-30322
This paper details our ongoing experience with field testing of copper naphthenate and other copper carboxylate preservative systems. Results from field stake tests at an AWPA Hazard Zone 4 test site are presented. In general, copper carboxylates made with ‘synthetics’ yielded results equivalent to or only slightly lower than systems with straight nap acids or nap acids amended with synthetic neo acid bottoms.
H M Barnes, M G Sanders, T L Amburgey

The leaching of copper, chrome and arsenate from CCA-impregnated poles stored for ten years in running water
1978 - IRG/WP 3122
There is no evidence to indicate that the chromium and copper components are leached from the outermost 5 mm of sapwood in poles impregnated with Boliden K33 and Tanalith C and stored in running water for ten years. The arsenic component, however, seems to be leached out during the first few months to an extent of about 20% of the initial amount. The leaching time is dependent on the preservative used.
F G Evans

Recent soft-rot research in softwoods and hardwoods
1980 - IRG/WP 1108
The purpose of this paper is to describe briefly the current status of our research on soft-rot fungi. The work to be discussed is still in progress and any results described must be regarded as provisional.
J A Butcher

A new concept of oxalic acid biosynthesis in physiology of copper-tolerant brown-rot fungi
2001 - IRG/WP 01-10394
Recently, a wide variety of roles of oxalic acid (oxalate) in wood decay systems have been receiving much attention. Copper tolerance of wood-rotting basidiomycetes has been believed to be due to the detoxification of copper wood preservatives by oxalate produced by these fungi. However, biochemical mechanism of oxalate biosynthesis in relation to physiology of wood-rotting fungi has not been elucidated although two oxalate-forming enzymes, oxaloacetase and glyoxylate dehydrogenase, have been studied in our laboratory. Recently, a new role of glyoxylate cycle in oxalate biosynthesis in wood- rotting fungi has been presented, and the cycle commonly occurred to varying extents among the fungi although they were grown on glucose. Enzymatic analyses showed that isocitrate was cleaved by isocitrate lyase in the glyoxylate cycle rather than oxidized by isocitrate dehydrogenase in tricarboxylic acid (TCA) cycle, and the fungi were found to lack a normal TCA cycle due to the absence of - ketoglutarate dehydrogenase. It is noteworthy that glucose was efficiently converted to oxalate in a theoretical yield of about 80%, accumulating in the culture media of F. palustris. The results further indicate that acetyl-CoA derived from glucose was not completely oxidized to CO2 in TCA cycle but was mainly converted to oxalate with help of the other coupling metabolic cycles, including glyoxylate cycle. Formation of oxalate from several intermediary metabolites using cell-free extracts of F. palustris confirmed that oxalate is also the final product of the metabolic pathway in the in vitro system. Thus, it is proposed as a new concept that most of copper-tolerant brown-rot fungi may acquire the energy by oxidizing glucose to oxalate, i.e. oxalate fermentation expressed in the following equation; Glucose + 5O2 --> 2 Oxalate + 2CO2 + 4H2O.
E Munir, T Hattori, M Shimada

Copper naphthenate performance: A new way to look at old data
2000 - IRG/WP 00-30215
Although copper naphthenate has over a 50-year test history, it is still considered as a "new" preservative in the United States when it is used for utility poles. It has also been extensively used in remedial treatments for poles and has considerable retail or over-the-counter sales. The test history includes a number of different tests and a rationale for evaluating this data and comparing the performance of copper naphthenate to other common pole preservatives is presented. Thus, the efficacy of copper naphthenate can be easily summarized.
C R McIntyre

The biostatic effect of copper on decay of fire retardant-treated mining timber
1991 - IRG/WP 1507
Blocks of Eucalyptus grandis were treated with 20kg/m³ ammonium sulphate as fire retardant and challenged with Coriolus versicolor. Replicates were soil buried. A second set of blocks was treated with retardant and copper at 6.6 kg/m³ (ie 1% w/w), and challenged similarly. After 8 weeks weight losses produced by Coriolus versicolor in untreated, retardant treated and copper supplemented blocks were 45, 25, and 0% respectively, and corresponding weight losses in soil were 27, 25 and 10%. These results, and electronmicroscopical observations, showed conclusively that Eucalyptus grandis treated with fire retardant was rapidly decayed, and that copper inhibited such decay.
G D Shelver, E A Shelver, A A W Baecker

Depletion of boron and copper from CCB treated test specimens using different leaching protocols
2004 - IRG/WP 04-50208
The objective of this study was to measure the depletion of inorganic wood preservative components regarding the proposed OECD guideline "Estimation of emissions from preservative-treated wood to the environment: laboratory method for wooden commodities exposed in the use class 4 and 5" as part of the project "Investigations concerning the influence of test parameters on the release of biocidal actives from treated timber in leaching tests". Pine sapwood specimens (50x10x150) were pressure impregnated with CCB according to European Use Class 4. Before leaching all samples were stores 4 weeks for fixation. In addition leaching tests were performed according to the European Standard EN 84 by means of EN 113 blocks. Parallel investigations were carried out between two laboratories to assess the repeatability and comparability of the methods. The results of chemical analysis of leachates taken at different time intervals show that similar depletion rates were determined for copper and boron independent on the leaching protocol used. However, the loss of copper as well as chromium in short term dipping experiments was often lower than the detection limit. Furthermore it can be stated that the difference between parallels was higher for the results which were obtained for the OECD guideline that EN 84. A comparison of both laboratory results indicate that a quite good repeatability is given in case of the CCB treated material.
E Melcher, R-D Peek, U Schoknecht, R Wegner

Light organic solvent preservative treatment of glue-laminated radiata pine
1986 - IRG/WP 3380
The high permeability of radiata pine (Pinus radiata D. Don) is associated with ray-tissue and in particular the cross-field pits linking ray-tissue to tracheids. This pathway is absent in the tangential grain direction, leading to poor preservative penetration when treatment is restricted to the radial face - for example, timber fabricated into glue-laminated beams.
P Vinden

Effectiveness and synergistic effects between copper and polymer betaine
1996 - IRG/WP 96-30097
Different formulations of "Copper Amine" and Polymer Betaine were studied. During laboratory tests a synergism between both active ingredients against soft rot and dry rot has been found. The efficacy against soft rot according to the "BAM method" and the European Standard ENV 807 depends only on the amount of copper. Long term tests in a fungus cellar for determining the relative protective effectiveness in ground contact show similar results as CCA-treated wood.
H Härtner, V Barth

Performance of Tebbacop in laboratory, fungus cellar and field tests
2000 - IRG/WP 00-30222
A novel organo-copper wood preservative ("Tebbacop") has been exposed to 12 years fungus cellar testing and 6 years above ground field testing. In the fungus cellar, Tebbacop at a retention of 0.053% Cu m/m oven dry wood out-performed CCA at a retention of 0.55% m/m oven dry wood. In above ground tests, L-joints treated to a Tebbacop retention of 0.012% Cu are performing as well as joints treated with TBTN to a retention of 0.08% Sn. In a slightly more severe decking test, 0.016% Cu as Tebbacop was more effective than 0.08% Sn as TBTN.
M E Hedley, D R Page, B E Patterson

A new wood preservative based on polymerized complexes of aminotriazole with copper acetate
1998 - IRG/WP 98-30169
This paper presents the results of preliminary fungitoxicity tests as carried out on new polymerized complexes of aminotriazole with copper acetate (PCC) against Coniophora puteana and Trichoderma viride. Laboratory tests on wood confirmed the findings arrived at in the screening test on agar medium. Deep penetration into pine wood of compounds studied was observed and particularly so at humidity above the point of fiber saturation (up to 10 mm in manual treatment), as well as good fixation in wood. Together with quaternary ammonium compounds (QAC) a strong synergistic effect towards the microorganisms tested was evident. The formulations investigated in the present study seem promising for future use in the wood preservation. Their practical implementation may enable effective control of wood destroying agents.
K J Krajewski, A Lukasiewicz, J Wazny

Leaching of copper, chromium and arsenic from CCA-treated Scots pine exposed in sea water
2000 - IRG/WP 00-50149
A laboratory leaching trial combining a static and a flowing seawater system was carried out to measure the leaching rates of copper, chromium and arsenic from the surface of Scots pine panels vacuum-pressure treated to 3, 6, 12, 24, and 48 kgm-3 CCA. Untreated and treated panels were exposed in flowing seawater for up to 8 weeks followed by 2 weeks submersion in static seawater which was taken for analysis. The study revealed a leaching hierarchy of Cu>Cr>As which supports the findings of other investigators. Over the 8 week leaching trial there was a time-related decrease in the rate of copper and chromium loss. Over the first week of leaching in flowing seawater, the rates of loss of copper and chromium decreased to between one-half and one-seventh, followed by lower rates of leaching over the remaining period of the investigation. In contrast, the rate of loss of arsenic from the wood appeared to increase slightly over the same period. The data are compared with minimal leaching rates of toxins from the surface of anti-fouling paints and are discussed in terms of the fouling communities which are established on Scots pine panels treated to similar target retentions.
C J Brown, R A Eaton

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