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Leaching of chromium and other cca components from wood-cement composites made with spent CCA treated wood
2000 - IRG/WP 00-50153
Wood cement composites are an attractive option for recycling spent treated wood, since the CCA treatment enhances the physical, mechanical and biological resistance properties of the composite. However, we have noted a higher than normal leaching of chromium from these products and this appears to result from conversion of some of the trivalent chromium to the more leachable and toxic hexavalent chromium from the trivalent chromium in the wood. The effects of hexavalent chromium reducer --FeSO4, the pH value of mixing water and different kinds of accelerators on the leaching properties of this composite were tested. Arsenic and copper components of CCA in treated wood were well fixed after mixed with cement. Although total chromium leaching amount was reduced greatly in the CCA treated wood-cement composite compared to CCA treated wood, more hexavalent chromium was detected from the leachate of the composite. Cr+6 leaching accounted for about 80% of the total chromium leaching. FeSO4 had a positive effect on decreasing chromium leaching amounts, especially when used in the board having more potentially leachable chromium. Reducing the pH value of mixing water decreased the total chromium leaching amount, but its effect on Cr+6 leaching was not significant. The leaching of Cr+6 and total chromium also depended on the accelerators used; boards with added CaCl2 showed less Cr+6 and total chromium leaching amounts, while Na2CO3 increased chromium leaching.
D Qi, P A Cooper

Chromium on the surface of CCA-treated wood
1978 - IRG/WP 386
Chromium in solutions of CCA preservatives is predominantly in the hexavalent state (Cr VI). It is well known that Cr VI is associated with dermatitis and skin ulceration in workers handling chromium containing products and processes. When reduced to the trivalent state, however, chromium is considerably safer. An essential part, therefore, of safety procedures in any chromium - using industry is the prevention of skin contact with hexavalent chromium. We carried out a series of tests to determine the influence of temperature on total chromium on the surface of treated wood and the amount of Cr VI in the total.
C R Coggins, P Hiscocks

Effectiveness of CCA fixation to avoid hexavalent chromium leaching
2002 - IRG/WP 02-50187
It is generally assumed that hexavalent chromium in chromated copper arsenate wood preservative is substantially reduced to trivalent chromium during fixation and that the potential to leach the more toxic CrVI is minimal. However, there are occasional claims some hexavalent chromium remains in wood after fixation and that small amounts of CrVI are available for leaching. One problem is that other metals such as iron can develop the same colour reactions as CrVI with the standard indicator, diphenyl-carbazide which may result in false measurements of CrVI. Ion chromatography can measure CrVI to 0.5 parts per billion and distinguish the reaction from that with other metals. In this study a number of CCA treated wood samples of different wood species and ages and wood cement and wood plastic composites containing CCA treated wood were collected and exposed to laboratory leaching. The leach water was analysed for CrVI and total Cr, Cu and As. For CCA treated wood and wood plastic composites, CrVI in the leachate was near or below the detection limit of the ion chromatograph (<1ppb) compared to total chromium levels of 200 – 2700 ppb. The amount of hexavalent chromium relative to total chromium leached was generally less than 0.1 %. Leachate from wood cement composites showed significant levels of CrVI (up to 50% of the total chromium leached). However, both hexavalent and total chromium levels in the leachate were low (0.2 – 0.4 ppm). These results show that once the CCA is properly fixed in wood, there is no health or environmental risk associated with toxic hexavalent chromium being released from treated wood.
P A Cooper, D Jeremic, Y T Ung

Wood preservation in Canada - Regulation and Registration
2001 - IRG/WP 01-50166-02
The Canadian wood preservation industry is at a critical juncture now as a number of initiatives converge on the industry over the next few years. Issues facing the industry include: Re-evaluation of the conventional wood preservative chemicals - inorganic arsenicals, creosote and pentachlorophenol targeted for July 2001. Delayed registration of new actives as a result of re-evaluation activity and priority. ?Implementation of the Environment Canada "Strategic Options" recommendations for preservative components considered "toxic" under the Canadian Environmental Protection Act, including hexavalent chromium, arsenic, PAH contaminated wastes, benzene hexachloride, dioxins and furans. Updating of the Technical Recommendation Documents for the design and operation of wood treating plants (now complete). The backgrounds, implementation, interactions and impacts of these initiatives on the Canadian Wood Preservation Industry are discussed.
P A Cooper

Results of chemical analyses in the field of wood preservation in the Bundesanstalt für Materialprüfung
1973 - IRG/WP 321
The results of qualitative and quantitative chemical analyses of wood preservatives are often the basis for evaluating the various works in the field of wood preservation. In the past 10 to 15 years a number of such works was carried out in the Bundesanstalt fur Materialprüfung, Berlin-Dahlem, dealing with the identification and effectiveness of wood preservatives and with methods of wood preservation. Fundamental realisations were made which will be summarised below. It seems advisable to differentiate between inorganic and organic chemical wood preservatives and methods of analyses. These are two distinct fields which differ also with regard to the analytical techniques applied.
H J Petrowitz

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

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

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

A discussion of current theories concerning CCA fixation
1983 - IRG/WP 3238
The understanding of the fixation mechanism of CCA and related preservatives in wood has been greatly improved by a significant series of recent scientific papers. In view of recent concerns in New Zealand regarding the long-term efficacy of CCA in high decay-hazard situations, it was considered appropriate to review this recent work and to contrast it with theories presented by previous workers.
D V Plackett

Developments in wood preservation
1977 - IRG/WP 393
The purpose of this paper is to comment very briefly upon recent developments and trends in wood preservation so that members of this Working Group have a basic knowledge of activities in other countries. The last paper was prepared in April 1976 and the present paper refers to developments, since that time.
B A Richardson

Collaborative field experiment: Analysis of copper and chromium in stakes of the four reference timbers
1982 - IRG/WP 3213
The stakes analysed belong to the Swedish set of the four reference timbers of the collaborative field experiment (Document No: IRG/WP/367). Before the field exposure 60 mm were cut off the end of each stake. This was done in order to be able to carry out chemical analyses as well as different types of testing. Some of the material has been used in softrot tests (Document No: IRG/WP/1151).
T Nilsson

Quantitative determination of Chromium: A comparison of three instruments
1995 - IRG/WP 95-50053
A comparison is made between three instruments for measuring levels of chromium in the leachate of copper-chrome-arsenic (CCA) treated timber. These include an atomic absorption spectrophotometer, an inductively coupled plasma spectrometer and the RQflexâ. The RQflexâ is a new hand-held instrument which measures chromium by dipping a ReflectoquantÒ strip into the leachate and inserting the strip into the RQflexâ. Readings are determined reflectometrically following a reaction between chrome and the Reflectoquantâ strip. It provides an inexpensive and quick technique which is used in this paper to determine the degree of preservative fixation prior to the removal of CCA treated timber from drip pads of wood treatment sites. The results indicate that RQflexâ is a suitable instrument for the rapid assessment of chromium levels in rain wash off from treated timber. A comparison is given of the economics and accuracy of the instruments for measuring chromium.
S Walley, P R S Cobham, P Vinden

Migration of active ingredients from treated timber into fresh water
1991 - IRG/WP 3669
Spruce roundwoods and segments were treated with three different wood preservatives. Two of them containing copper and chromium the other one free of chromium. After fixation (3 weeks, 20°C) the specimens were leached by using artifical rain or by shaking the segments for one hour in contact with demineralized water. The water was analysed for the relevant elements of the preservative tested. Leachability of the components from the copper-chromate treated wood decreases. After 4-8 leaching cycles an almost constant migration of wood-preservatives, depending on the leaching method and the pH-value of water applied, was determined for the chromate containing preservatives. In the course of leaching cycles a constant rate of migrated copper from the preservative free of chromium was determined after 4 - about 17 leaching cycles. After 16 leachings of the segments the leached copper as calculated on the copper retention was determined to 1.6 - 5% for the chromium containing preservatives and about 22% for the tested variation of the new type of preservative.
H Klipp, H Willeitner, K Brandt, A Müller-Grimm

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

Lignin-copper, a new wood preservative without arsenic and chromium
1992 - IRG/WP 92-3702
A more environmentally sound treatment for wood with preservatives containing no arsenic or chromium, has been developed and studied on a laboratory scale. The method involves a first step impregnation with an aqueous solution containing modified, water-soluble kraft lignin followed by a second step involving impregnation with a copper salt solution to give fixation of the lignin into a water-insoluble form and to achieve complementary protection. The two steps can be performed without intermediate drying of the wood in a conventional reactor for vacuum-pressure impregnation. The treatment has been shown to give good protection against degrading fungi, tunnelling bacteria and termites, and a lower growth of mould on the wood surface. Field tests (NTR test) indicate, after 4 years of exposure, very good protection gained by this new treatment. Fibre and particle boards made from wood fibres and wood particles, treated with this method show increased dimensional stability and rot resistance.
B Ohlsson, R Simonson

Examen chimique du traitement de poteaux effectué à St-Michel s/Meurthe
1974 - IRG/WP 337
J Guillemain-Thévenot, C Jacquiot

Protecting wooden structures
1980 - IRG/WP 392
Chromium-containing chemicals that effectively retard weathering of wood improve performance of subsequently applied finishes. Current work is focusing on the performance of wood-derived products (plywood, hardboard, fiberboard, particle board) after surface treatment with inorganic chemicals. The overall objective of the continuing research is to investigate new environmentally safe procedures to stabilize wood surfaces and to improve performance of applied finishes.
W C Feist

CCA fixation experiments. Part 2
1989 - IRG/WP 3505
CCA fixation in wood was measured by both squeezing solution from treated wood that had not been dried and analyzing the solution for copper, chromium and arsenic, as well as using a chromotropic acid test to detect the presence of chromium VI. Both methods provide useful information on the CCA fixation process and illustrate that chromium VI disappears as CCA becomes fixed within wood.
W S McNamara

Investigation of the fixation in wood of chromated zinc chloride and copperised chromated zinc chloride preservatives
1976 - IRG/WP 372
A biological method of evaluating the extent to which CZC and CCZC preparations are retained in wood in terms of the potential protection which they afford against destruction by Merulius lacrymans (dry rot) is given. CCZC is recommended for protection of wood under moderate leaching conditions, while the use of CZC under such conditions is not recommended.
V N Sozonova, D A Belenkov

Assessment of contamination of soil and water at a CCA treatment plant: A demonstration project
1996 - IRG/WP 96-50067
Soil, sludge, dust and water samples were collected at a copper/chromium/arsenic wood preservation plant. Contamination of soil, sludge, dust and surface water with copper, chromium and arsenic was detected. Levels of contamination were sufficiently high to require remediation. Contamination originated from preservative solution dripping from recently treated wood. Migration of contaminants was via surface water run-off; poor housekeeping and operational procedures; forklift movements and wind-blown dust.
P N Durrant, D C R Sinclair, G M Smith

Fungal degradation of wood treated with metal-based preservatives. Part 2: Redox states of chromium
1996 - IRG/WP 96-10164
Concerns have arisen about the leaching of heavy metals from wood treated with metal-based preservatives, such as chromated copper arsenate (CCA). Of particular concern is the toxic redox state of chromium and arsenic in aging and decayed CCA-treated wood. Generally, hexavalent chromium is more toxic than trivalent chromium and trivalent arsenic is more toxic than pentavalent arsenic. The desired outcome from treating wood with CCA is total change of Cr(VI) to Cr(III) and As(III) to As(V). As part of an on-going study to determine the fate of copper, chromium and arsenic during aging and decay of CCA-treated wood, we detected Cr(III) and Cr(VI) in situ in CCA-treated southern yellow pine lumber. The redox states of Cr were determined using synchrotron X-ray fluorescence spectroscopy (SXRF). An SXRF microprobe was used to to detect Cr redox states by measuring X-ray absorption near-edge structure (XANES). The ratio of Cr(III) to Cr(VI) was determined (1) on the surface and interior of lumber two years after CCA treatment and (2) in lumber during decay by a CCA-tolerant fungus, Meruliporia incrassata TFFH-294. The XANES spectrum for Cr(VI) has a strong pre-edge feature that is not present in the spectrum for Cr(III). Only the Cr(III) XANES spectrum was detected on the surface and in the interior of the wood, indicating total reduction of Cr(VI). The XANES spectrum for Cr(III) was detected in wood after 12 week decay by Meruliporia incrassata TFFH-294, indicating that the fungus does not oxidize Cr(III) to Cr(VI) during the decay process. We are currently using XANES spectroscopy to detect and map in situ redox states of As in CCA-treated wood.
B Illman, S Bajt, T L Highley

Literature survey on the permanence and distribution of salt-type wood preservatives
1969 - IRG/WP III 1B
The objective of this survey is generally to review some of the more important published work dealing with the distribution and permanence of salt-type waterborne wood preservatives in treated timber. The survey is limited to the major chrome-containing formulations and the classification system proposed by Becker (1964) has been adopted throughout. CK - chromium, copper (copper, chrome); CKA - chromium, copper, arsenic (copper, chrome, arsenate); CKB - chromium, copper, boron (copper, chrome, boron); CFK - chromium, fluorine, copper (copper, chrome, fluorine); CFA - chromium, fluorine, arsenic (fluor, chrome, arsenate); CF - chromium, fluorine (fluor, chrome). The literature compilation covers the performance of these preservatives assessed from laboratory tests, field tests and practical experience; their application and distribution in the treated wood; and their influence on materials such as glues, paints or metals and the wood itself. It is not the purpose of this survey to draw conclusions regarding the relative merits of the various formulations, the choice of a formulation in a given situation depending upon many factors outside the terms of reference of this review, and not all of a technical nature. In general, there is insufficient directly comparable data for a definitive assessment and in the few comparisons available special factors frequently apply.

Disposal of CCA treated waste wood by combustion - An industrial scale trial
1996 - IRG/WP 96-50068
Totally 272 m³ (62.7 t) of CCA treated utility poles were chipped and incinerated at Jalasjärvi Gasification Plant. In average the whole batch of chips contained 57 kg of elementary copper, 95 kg chromium and 76 kg arsenic. During the 56 h combustion trial the measured arsenic emission to the air was 76 g in total. Copper and chromium emission was less than 1 g. The condensing water from the cooling unit and the ash from the gasifier were collected and transported to Outokumpu Harjavalta Metals Oy and finally circulated through a copper refinery line.
A J Nurmi

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

The course of fixation of Cu-Cr-As wood preservatives
1972 - IRG/WP 307
Copper-chrome-arsenic (CCA) preservatives in contact with wood result in an instant extensive increase of pH, because of ion-exchange and adsorption reactions with the wood. During precipitation of the active elements the pH continuously increases but reaches a maximum, when all chrome is consumed. Some of the early reaction products are unstable and slowly convert via dissolution into stable compounds. The conversion proceeds by proton liberating as well as proton consuming reactions. The pH therefore alternatively decreases and increases until the reactions cease after several months. The final equilibrium fixation products are: ion-exchange fixation of Cu to the wood CrAsO4, Cu(OH)CuAsO4 and Cr(OH)3. The chrome fixation is 2nd order with respect to hexavalent chrome in the liquid phase, four regions with distinct chrome fixation rate constants were found. A hypothesis is given for the mechanism of fixation.
S-E Dahlgren

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