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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

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

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

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

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

Leaching of Active Components from Preservative Treated Timber. Stage 1: Semi-Field Testing
2004 - IRG/WP 04-20302
The project is aiming at finding realistic leaching rates from preservative-treated wood in use class 3 (above ground). The project focuses on developing a field trial method for investigating leaching. Panels are subjected to outdoor exposure under natural weather conditions at a test field at the Danish Technological Institute. The leachate is collected and monitored by chemical analysis of the active ingredients. The project is ongoing and the paper presents results from approximately 12 months’ of exposure. The study includes commercially available organic and inorganic fungicides using 4 different application methods: vacuum-pressure-, double-vacuum-, flow coat and supercritical treatment. Different test set-ups examine the influence of a number of different parameters. The results obtained from outdoor exposure will be compared with a laboratory test method (proposal of CEN/OECD, DOC TC38 WG 27 N039). The method investigated has proved to be useful in characterising the leaching behaviour from preservative-treated wood. The results from the present project are intended to serve as part of the basic documentation according to Directive 98/8/EC (The Biocidal Products Directive, BPD) for leaching of active ingredients in use class 3.
N Morsing, B Lindegaard

A laboratory soil-block decay evaluation of plywoods edge-treated with preservatives
1982 - IRG/WP 2174
Preservative-treated plywood used under conditions or severe decay hazard frequently has its original, or cut edges, protected by the application of a field-cut preservative. This study uses a laboratory test method to compare the efficacy of four commercial preservative treatments against two commonly occurring brown-rot fungi. The results are not meant to indicate the service life of such treated plywood.
R S Smith, A Byrne

Rapid leaching test
1991 - IRG/WP 2367
An accelerated test which is suitable for measuring the extent of metal fixation in both chromium and non chromium containing preservatives is described.
J A Cornfield, M Bacon, A Lyman, C Waldie, M R Gayles

The influence of previous anti-blue-stain preservative treatments on the fixation of CC in spruce
1997 - IRG/WP 97-30134
Freshly cut and kiln dried spruce boards were treated with 4 different anti-blue stain preservatives (ABP). After a period of 10 days allowing the samples to dry and fixate, the samples were treated with CC (chromium, copper formulation) using a vacuum pressure cycle. After impregnation the wood was steam fixed. A submersion leaching test showed differences in the leachable quantity of copper and chromium. When related to the retention of both salts after impregnation, no differences could be found between samples previously treated with anti-blue-stain preservatives and untreated samples. However, the retention of CC diminished significantly by application of quaternary ammonium compounds.
M Van der Zee, W J Homan

Metal carboxylates for wood pest control
1996 - IRG/WP 96-30109
Metal carboxylates have been used as wood preservatives for more than fifty years. Predominantly salts of naphtenic acids have been commercially applied so far. They have water repellent as well as fungicidal and insecticidal properties. In the last years, metal carboxylates of saturated fatty acids were introduced. Fatty acids with 7-10 carbon atoms already have fungicidal activity by themselves. However, their efficacy is markedly increased in a complex with metal ion such as copper and zinc. This carboxylates are environment friendly and low toxic for humans. We studied fungicidal, insecticidal and termiticidal effectiveness of copper and zinc carboxylates by European standard methods. The strongest fungicidal and insecticidal activity showed copper and zinc naphtenates and copper octanoate. The metal octanoates are soluble in white spirit and, moreover in aqueous ammonia solutions. One day after treatment, the leaching of some carboxylates from wood was very low. These carboxylates did not increase the flammability of treated wood.
F Pohleven, M Petric

EPR investigations of interactions between ammoniacal Cu(II) octanoate and wood
1996 - IRG/WP 96-30110
Ammoniacal solutions of copper(II) octanoate [ C u . h l f . 2 . r h l f.(O2CC7H15)4], interactions of these solutions with wood and wood components, and leaching of copper(II) octanoate from impregnated wood samples, have been studied by electron paramagnetic resonance (EPR) method. It is still not clear if in the Cu(II) octanoate - water - ammonia system, Cu(II) remains in a (copper(II) octanoate - ammonia) complex. The majority of leached Cu(II) with distilled water and a solution simulating acid precipitations was washed out in the first five hours of leaching procedure (up to 35% of initial Cu(II)). Time dependence studies of interactions of ammoniacal Cu(II) octanoate with wood, cellulose and brown rotted lignin showed, that the fastest and most significant was the reaction with lignin. Cu(II) is immobilised also on cellulose. A significant contribution of ammonia evaporation to the fixation mechanism of the preservative was observed as well.
F Dagarin, M Petric, F Pohleven, M Sentjurc

Leaching of copper, chromium and arsenic from CCA-treated slash pine heartwood
1994 - IRG/WP 94-50020
Drying green slash pine with any of three high temperature drying schedules produced a product in which both the sapwood and the heartwood could be penetrated with CCA using a modified Bethell treatment schedule. Required H3 retentions were achieved in both sapwood and heartwood, from 200 litres per m³ charge uptake. Post-treatment fixation/drying was accomplished by three different regimes, including an accelerated fixation. Although acceptable preservative penetration and retention was achieved in the heartwood, arsenic fixation (as determined by both AWPA procedure E11-87 and U.S. EPA TCLP procedure) was inferior to that attained in the sapwood. TCLP leachates from 1 cm³ heartwood blocks contained up to 4.5 mg/l arsenic, very close to the maximum value (5.0 mg/l) currently permitted in Australia for arsenic waste disposal. Though there are clear advantages in achieving heartwood penetration, caution must be exercised to ensure that this step does not compromise the accepability of the product. No process modification could be accepted if it introduced possibilities of exceeding safe disposal limits for sawdust and offcuts, or building site contamination.
M J Kennedy, G Palmer

Chemical analyses of IRG/COIPM INTERNATIONAL MARINE TEST (to determine the effect of timber substrate on the effectiveness of water-borne salt preservatives in sea-water) samples
1987 - IRG/WP 4114
Chemical analysis of CCA and CCB treated timber was carried out after exposure at tropical and temperate marine sites. Results indicated that losses of all elements had occurred. In particular, losses of boron were severe. Arsenic and copper were also lost. The chromium components in both formulations was the most dominant metal remaining. The results suggest that chromium modification was important in timber treatments for the marine environment, since there appeared to be little difference in timber protection between the CCA and CCB systems.
L E Leightley

A comparative study of CCA type C and B treated poles in service
1993 - IRG/WP 93-50001-05
CCA K33 type B and C treated utility poles, 9 pieces of each treatment type, were analyzed for preservative retention after 11 years in use. Borings were taking 1 m above and 0.3 m below the ground line. Also total amount of copper, chromium and arsenic was determined in soil surrounding the poles. The solubility of these active components in soil was monitored by using different leaching procedures. Remarkable losses of Cu, Cr and As were found in both type of poles, particulary As from type B poles. Exact figures could not be given because of missing original preservation data. In comparison to the natural background high As and Cu contents were found in soil. CCA type B poles emitted As up to 760 mg/kg (oven dried soil) which is least 760 times higher than the natural background (0.4-1.0 mg/kg). The average value of As emitted by C type poles was 92 mg/kg. The amount of copper varied from 10 to 50 fold to the background but no essential differenceswere noticed among the two groups. Type C poles emitted more Cr but the average figures were lower than that with As and Cu. The solubility of As, Cu and Cr, as a very important factor, was investigated by preparing series of leaching tests. Only slight differences were found between EPA (US Environmental Protection Agency) and water leaching tests. In both leaching tests As was the most soluble element and 1.2-1.1 mg/l of As in the soil connected to B type poles was in soluble form. The figures were much lower with the case of C type poles and were 0.16-0.26 g/l respectively. Additional tests also proved that lower pH values decreased the solubilily of As. The effect was even stronger with adding ferrous sulphate. On the contrary increases pH resulted higher solubility.
A J Nurmi

Leachability And Decay Resistance of Copper-Treated Wood
2004 - IRG/WP 04-30337
Samples of scots pine sapwood (Pinus sylvestris L.) were treated with solutions of (Copper II sulfat-5 hydro + fluoroboric acid) and (Copper II sulfat-5 hydro + fluoroboric acid + boric acid) in order to determining to leachability and decay resistance against brown rot fungus (Postia placenta) and white rot fungus (Coriolus versicolor). Results indicated that the copper in treated wood is less strongly bound because of the higher copper concentration in the leachates from treated wood and leaching rate of Cu is highest initially and decrease over time. After leaching, however, weight losses increased because of the leaching of copper and boron compounds from wood, revealing a lower decay resistance.
A Temiz, T Nilsson, I Deemirtas, Ü C Yildiz

Leaching Characteristics of Copper in Copper Treated Wood
2003 - IRG/WP 03-30316
The leaching characteristics of copper in copper treated bamboo and other wood species such as slash pine and poplar has been conducted in this paper according to AWPA M11-87 standard, the result indicates that: --Copper fixation rate of salts from organic acids such as citrate and oxalate and malate is less than other non-organic acid formulations. --Copper fixation rate of oven-dried bamboo samples is less than air-dried bamboo samples for all formulations containing copper. --Copper fixation rate of bamboo treated with ACQ containing dimethyl didecyl ammonium chloride (DDAC) is higher than other type of ACQ formulation containing benzalkonium chloride. Copper fixation rate of ammonia-based ACQ-B treated bamboo is higher than amine-based ACQ-D while in the same retention level. --Copper fixation rate in some formulations containing phosphate is higher than non-phosphate ones.
Mingliang Jiang, Junliang Liu, Daochun Qin, Yamei Wang, Zehui Jiang

Leaching and fixation characteristics of chrome-copper-fluoride-zinc (CCFZ) treated wood
1996 - IRG/WP 96-30096
The leaching characteristics of radiata pine sapwood blocks treated with CCFZ were evaluated by the AWPA standard leaching test. The rate of fixation of the preservative components in CCFZ treated radiata pine were also evaluated by quantitative analysis of solution expressed from the treated wood. Both leaching and fixation characteristics of CCFZ were compared with CCA-Type C treated wood samples. The permanence of CCFZ is excellent and comparable to that of CCA-Type C, and the rates of CCFZ fixation were similar to those found for CCA-Type C. These results suggest that CCFZ has a potential as alternative preservative for the replacement of CCA-Type C.
Gyu-Hyeok Kim, Jong-Bum Ra

Applications of the shower test. Part B: Results from CC and CCB treated wood: influence of fixation process
1993 - IRG/WP 93-50010
This report outlines the results of shower tests conducted on CC and CCB treated wood. The results indicate the fairly good fixation of chromium and the reasonable fixation of copper in CC and CCB formulations, as judged by the leaching limits within the Environmental Regulations. In general boron leaches to a higher extent than chromium and copper. The shower test has proven to be a useful quality control and research test. It determines reasonably accurately the leaching under simulated conditions and, admittedly from a limited number of tests, it can determine differences between various fixation cycles. Natural fixation, controlled climate room fixation and steam fixation were compared. Overall the sleam fixation process gave the lowest leaching figures although the selection of an appropriate fixation facility is a question for individual companies, taking into account capital, customer base, throughput etc.
W J Homan, H Militz

Susceptibility of CCB treated wood to fungal colonization
2003 - IRG/WP 03-10492
CCB treated wood is generally resistant to all wood decay fungi. However, like CCA impregnated wood, susceptibility of CCB treated wood to copper tolerant fungi have been observed. The ability of various brown rot fungal hyphae to penetrate and overgrow the wood samples was investigated. Samples made of Norway spruce (Picea abies) were impregnated with 5 % CCB solution according to the EN 113 procedure. After conditioning, part of the samples was leached according to the EN 84 method. Small stick of unimpregnated wood (r = 1.5 mm, l = 25 mm) was inserted into a hole, bored in the center of the samples, and after that sealed with epoxy coating. Sterilized, leached and non-leached impregnated and unimpregnated specimens were exposed to two copper-tolerant (Antrodia vaillantii, Leucogyrophana pinastri) and two copper sensitive (Poria monticola, Gloeophyllum trabeum) brown rot fungi for one, two or four weeks. After exposure, the inserted wood pieces were removed from the specimens and put onto nutrient medium in petri dishes. Growth of the hyphae from those wood pieces was then visually determined. Rate of colonization by the fungi were determined by measurement of CO2 production. After that, mass losses of parallel specimens were also determined. The fastest colonization of the unimpregnated specimens was by G. trabeum (one week). On the other hand, no fungal growth could be detected on non-leached CCB impregnated specimens even after four weeks of exposure. However, significantly more intense colonization by the copper tolerant fungi were detected on the leached CCB treated samples.
F Pohleven, U Andoljsek, P Karabegovic, C Tavzes, S A Amartey, M Humar

Copper leaching from Kemwood ACQ and Embalit CBC treated wood products
2000 - IRG/WP 00-50150
TNO has performed a study on the leaching of copper from Kemwood ACQ and Embalit CBC treated wood products, further referred to as ACQ and CBC. The sawn dry wood has been impregnated using an industrial vacuum-pressure process with ACQ (with or without Ultrawood 4) or with CBC, under supervision of Flexchemie B.V. After treatment samples have been transported and subjected to leaching tests at TNO. The leaching tests applied were a submersion test according to NEN 7345 and shower tests according to a fixed protocol (Havermans et al., 1993). Parallel to each shower tests two or three screening tests for leaching have been performed, according to the existing guideline (BRL 0601, 1999) and according to experimental spray and submersion protocols. The screening should indicate, if the leaching limits of the guideline are likely to be met or not. The results of the screening leaching test have been plotted against the results of the shower tests. It has shown that the existing leaching limit for the "standard" guideline screening test of 0.5 mg copper per ml. is too low and does not indicate if the wood will perform well in the shower test, for both ACQ and CBC treated wood. The experimental spray test has shown to be fairly good as prediction for compliance in the shower test. Furthermore the submersion test according to NEN 7345 has shown promising reductions with a factor 3,7 of copper leaching in ACQ and Ultrawood 4 treated Norway spruce compared to an earlier test with ACQ treated Scots pine. The copper emission in CBC treated Scots pine was a factor 2,5 higher compared to the ACQ-Ultrawood 4 treated Norway spruce.
P Esser, W L D Suitela, H Trompetter

The influence of soil pH on leaching of CCA elements from pressure-treated Eucalyptus saligna sapwood: environmental implication
2003 - IRG/WP 03-50203
Evidence is accumulating as to poor distribution and fixation of CCA in tropical hardwoods, and there is therefore a necessity to investigate the permanency of CCA in tropical hardwoods. The relationship between soil pH and leaching of Cu, Cr and As from CCA pressure-treated sapwood of Kenyan-grown Eucalyptus saligna was tested under laboratory conditions. Small sapwood samples were pressure-treated with 6% CCA-C (oxide type) to a retention of 25.4 Kg/m3, and leached with mild agitation in soil-extract water representative of soil pH 3.5, 4.5, 5.0, 7.5, 8.5, and in tap water (pH 6.8), for 3, 6, 9, 12, 15 and 18 days under controlled laboratory conditions. The results revealed that leaching of Cu, Cr and As was generally high under acidic conditions, low under alkaline situations and lowest at neutral pH. After leaching for 18 days at pH 3.5, average extraction of Cu, Cr and As was respectively 60.8 ppm, 51.3 ppm and 53.8 ppm. Leaching at pH 6.8 extracted low average amounts of Cu, Cr and As, being 0.15 ppm, 0.25 ppm and 0.42 ppm respectively. At pH 8.5 losses were Cu: 1.9 ppm, Cr: 2.4 ppm and As: 1.4 ppm. The patterns of leaching of the elements were irregular in relation to pH and the order established after 18 days of leaching was Cu>As>Cr at pH 3.5, As>Cr>Cu at pH 6.8 and Cr>Cu>As at pH 8.5. Apart from the influence of pH alone, the chemical, physical and microbiological properties of the soil-extract water used may also have influenced leaching. The results indicate that CCA-treated E. saligna used in ground contact, especially in acidic soils, may lose significant amounts of Cu, Cr and As to the environment. The environmental risks that the large number of CCA-treated hardwood poles and posts used in tropical soils represent raise the question as to whether CCA should remain the preferred wood preservative for tropical hardwoods, especially the eucalypts.
R Venkatasamy, D N Okwara

Fixation of copper-chrome-arsenic treated timber: A comparison of leaching methodologies
1996 - IRG/WP 96-50075
Five packs of kiln dried radiata pine heartwood were treated with copper-chrome-arsenic preservative treated, utilising a modified Bethell treatment schedule. Two methods of determining the level of preservative fixation were compared. These included the diphenylcarbazide method and simulated rainfall testing. The fixation levels were generally higher for tests involving simulated rain leaching. Fixation of copper-chrome-arsenic determined by the diphenylcarbazide method was found to fluctuate with time. Localised surface concentrations of preservative, 'hot spots', were suggested as the cause. Simulated rainfall appeared to provide a more realistic assessment method for determining potential preservative leaching of multisalt preservatives.
S Walley, P R S Cobham, P Vinden

A comparison of the leaching resistance of diammine-copper complexes and copper carbonate precipitated in wood
1997 - IRG/WP 97-30158
Previous studies have shown that during treatment of wood with ammoniacal copper solutions, both simple copper precipitates and diammine-copper complexes are formed. The objective of the present study is to determine the relative importance of both forms of copper, on such aspects as preservative leachability and biological performance. In the current experiment, the leachability of copper carbonate precipitated in wood is compared with that of diammine-copper complexes. The results confirmed that both forms of copper resisted leaching by distilled water. However, when exposed to the more aggressive leaching conditions using the sodium citrate buffered solution, the diammine-copper complexes were significantly more ressistant to removal from the wood. Further studies are planned to examine the diammine-copper complexes present in the wood as well as the efficacy of these complexes against wood decay fungi.
Xiao Jiang, J N R Ruddick

Copper linoleate: A new low toxcity wide spectrum, heavy duty wood preservative
1995 - IRG/WP 95-30082
Copper linoleate, a "fixed" copper soap has been developed and evaluated in South Africa over a 30-year period. The initial product, an organic solvent based preservative has been tested in pine poles against termites and fungi. Results indiate that the product has performed well against existing heavy duty wood preservatives such as CCA and creosote in long term field trials (30 years). The paper describes the basic formulation of copper linoleate and the reaction and possible fixation mechanisms of copper linoleate with wood lignin. The paper moves on to describe further work on an emulsifiable version of copper linoleate for use as a water borne wood preservative. The performance of this product is evaluated in accelerated trials to obtain comparative performance data. The emulsion-based product addresses a need for a low-toxicity, waterborne, heavy duty wood preservative. The paper also considers some of the physical properties of the product and outines the remaining barriers for its industrial commercialisation.
D Conradie, P Turner, W E Conradie, A J Pendlebury, T Pizzi

The mechanism of leaching of copper-chrome-arsenic preservatives from treated timber in saline waters
1976 - IRG/WP 374
A mechanism for the leaching of copper-chrome-arsenic preservatives is proposed on the basis of theoretical calculations and experimental studies using timber subjected to a range of water types of different ionic compositions. Complex formation by copper (II) and chromium (III) with chloride and hydroxide ions is shown to affect the leaching rate. Of even greater importance is the salt effect on the activity coefficients. The various complexes formed at different pH values are discussed. Two minima are observed in the plot of copper leaching versus water salinity; these are attributed to the presence of the copper fixation compounds Cu2(OH)AsO4 and Cu3(AsO4)2. At low salinities NaCl is shown to have a coagulating effect on the copper fixation compounds, reducing their solubility, whereas at higher salinities complex formation dominates. With chromium the coagulation effect is not observed and leaching increases with increasing salinity. Loss of arsenic is shown to lag behind that of copper and chromium and is related to the chromium excess in the preservative formula: the greater the excess, the longer the delay in arsenic loss. The suggested mechanism adequately explains the experimental results.
J Irvine, S-E Dahlgren

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