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Recovery of copper chromium and arsenic from old CCA treated commodities
1998 - IRG/WP 98-50118
Due to the expected increase in spent treated wood over the next several decades, numerous means to reuse and recycle preserved wood have been proposed. Burning this wood for cogeneration or recycling of CCA treated wood into reconstituted composites are possible methods, but they are limited to laboratory scale because of environmental air emission issues and the manufacturing process. In the available literature, laboratory removal of CCA from treated wood has been conducted on 20 mesh size particles or saw dust. This approach requires chipping and grinding of lumber and poles into particles and saw dust. In the current study, about 95 to 100% copper, chromium, and arsenic were removed from 2 by 4's and pole sections without substantial modification of initial sample size. This extraction yield was obtained within 18 hours at temperatures ranging from 80- 100EC using a combination of citric acid and chelating agent at pH 4.
D P Kamdem, Wanli Ma, Jun Zhang, J Zyskowski


Recovery of copper, chromium, and arsenic compounds from the waste preservative-treated wood
1991 - IRG/WP 3651
In Japan, about 40 percents of waste wood is incinerated and the residue is dumped into the landfill site. The waste preservative-treated wood, which is mixed in nontreated wood, is incinerated in the same way, too. However, it will cause the serious problems that the gases contained with high concentration arsenic compounds are discharged from the smokestacks of the incineration facilities and the toxic water with high concentrations of copper, chromium, and arsenic compounds is discharged around landfill sites because the residue contains a lot of these compounds. To solve these problems, it is necessary to develop a method to recover these compounds from the waste preservative-treated wood. In this paper, extraction experiments of copper, chromium, and arsenic compounds from treated wood were carried out and evaluated as a method to recover these compounds. Through the experiments, suitable extractant, its concentration, and extraction conditions such as the temperature, extraction time, and the size of test wood piece were obtained. As the results of these experiments, Cr, Cu, and As compounds in the test wood piece were completely recovered into the extractant under the suitable conditions.
A Honda, Y Kanjo, A Kimoto, K Koshii, S Kashiwazaki


Recycling and disposal of timber treated with waterborne copper based preservatives
1993 - IRG/WP 93-50008
Recycling and disposal technologies are briefly reviewed. Details are given of chemical extraction techniques suitable for recovery of copper from timber treated with a new copper based preservative, and traditional chromium based products. Details of thermal decomposition tests according to the DIN 53436 protocol under flaming and non-flaming conditions are given. The decomposition products were analysed for C0, CO2,O2, NOx and arsine. Preservative treated timber showed higher mass loss than untreated timber at 400°C indicating that oxidation was promoted by the presence of preservative at this temperature. At 800°C, 99% mass loss occurred in all cases. Gas analysis showed little difference in combustion products and oxygen uptake between treatments at both temperatures. No arsine gas was detected in the decomposition products of CCA treated timber. A further series of burning tests was carried out to determine the fate of the heavy metals in treated timber samples during thermal decomposition, and to determine suitable extraction techniques to recover the metal for recycling from the residual ash. Using a new copper based preservative the residual copper in the ash had very low water solubility, whereas quantitative extraction could be obtained using acidic extraction techniques. Findings regarding arsenic recovery from CCA treated timber were comparable with those reported by other workers.
J A Cornfield, S Vollam, P Fardell


Rapid Microwave-Assisted Acid Extraction of Metals from Chromated Copper Arsenate (CCA)-Treated Southern Pine Wood
2009 - IRG/WP 09-50262
The effects of acid concentration, reaction time, and temperature in a microwave reactor on recovery of CCA-treated wood were evaluated. Extraction of copper, chromium, and arsenic metals from chromated copper arsenate (CCA)-treated southern pine wood samples with three different acids (i.e., acetic acid, oxalic acid, and phosphoric acid) was investigated using in microwave reactor. Oxalic acid was effective in removing 100% of the chromium and arsenic at 160°C and 30 min., and acetic acid could remove 98% of the copper and arsenic at the same conditions. Oxalic acid greatly improved the extraction efficiency of arsenic and chromium when time was prolonged from 10 min. to 30 min. Acetic acid also showed improved ability to remove arsenic and copper when the reaction temperature was increased from 90°C to 160°C.
Bin Yu, Chung Y Hse, T F Shupe


Microwave-Assisted Organic Acids Extraction of Chromate Copper Arsenate (CCA)-Treated Southern Pine
2010 - IRG/WP 10-50267
The extraction effects of acid concentration, reaction time and temperature in a microwave reactor on recovery of CCA-treated wood were evaluated. Extraction of copper, chromium, and arsenic metals from chromated copper arsenate (CCA)-treated southern pine wood samples with two different organic acids (i.e., acetic acid and oxalic acid) was investigated using a microwave reactor. Oxalic acid was effective in removing 100% of the chromium and arsenic at 160ºC and 30 min. reaction time. Acetic acid could remove 98% of the copper and arsenic at the same condition. Oxalic acid significantly improved the extraction efficiency of arsenic and chromium when time was prolonged from 10min. to 30min. The HSAB (Pearson acid base concept) concept was applied to explain why oxalic acid removed more chromium and less copper compared with acetic acid. Acetic acid also showed an improved ability to remove arsenic and copper when the reaction temperature was increased from 90ºC to 160ºC.
Bin Yu, Chung Y Hse, T F Shupe


Dual Borate and Copper Naphthenate Treatment of Bridge Timbers:- Potential Performance Enhancements and Cost Savings
2017 - IRG/WP 17-40797
Dual treatment technology combining diffusible preservatives with oil borne preservatives, widely used for crossties in the USA, has now also been commercialized with bridge ties/timbers. In order to understand the implications of these changes, the historic service life of creosote treated bridge timbers in northern and southeastern USA were considered as well as field test data for both creosote and copper naphthenate. These were used to estimate potential future service life. Estimates on life expectancy with added borates were also made from published data on performance. Cost benefit analysis based on creosote and copper naphthenate costs as well as assumptions made from field test efficacy data suggest cost savings of up to $20 per timber per year of additional service. Service life extension and the resulting cost savings could be achieved in a number of ways: change preservative from creosote to copper naphthenate; increase active ingredient retention; and/or add dual treatment protection. A preservative change from creosote to copper napthenate would be the simplest and lowest cost way of increasing service life of bridge timbers, with potential savings to both treater and railroad. An increase in copper retention could also give significant life extension, could be carried out at little additional cost and without increasing bleeding. The addition of borate to protect the heartwood also provides significant assumed increase bridge tie life, and can be used with either creosote or copper naphthenate treatments.
J Lloyd, C Brischke, R Bennett, A Taylor


A Green and Novel Technology for Recovering Copper and Wood from Treated Wood Waste – Part II: Optimization, copper metal recovery, and process design
2017 - IRG/WP 17-50326
The US consumes 70 million pounds of copper and produces 580 million cubic feet treated wood annually. The EPA disallows burning and reusing treated wood waste due to health/environmental concerns. Vast quantities of copper and wood are landfilled. Two safe and low cost extraction systems, citric acid and ammonium citrate, were identified in Part I of this study. In Part II of the study, effects of extraction conditions such as time, temperature, and equilibrium copper concentration were determined. More than 95% of copper was removed either at ambient temperature for 8 hours or at 40oC for 4 hours. The resulting solution was used in consecutive extractions with new batches of wood until copper reached its rate limiting concentration. The study demonstrated that copper in the extraction solutions could be electroplated onto various metal surfaces, thus efficiently recovered. This process regenerated aqueous solutions to be reused for future extraction. A chemical/engineering process was developed with this study for extracting copper from treated wood wastes, recovering copper from extraction solutions by electroplating, and cyclic use of regenerated aqueous solution. This green and novel technology can keep copper and wood from the landfill and bring tremendous environmental, economic, and social benefits.
S Chen, R Patel


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


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