Effects of delayed drying and CO2 application on copper amine fixation in ACQ treated red pine

Fixation of copper and amine in alkaline copper quaternary (ACQ-C) wood preservative was investigated to determine the effects of delayed drying and application of CO₂ gas under pressure. Unlike the fixation of CCA preservative, where the rate of fixation reaction is slowed down by evaporative cooling during drying, delayed drying of ACQ treated wood had no observable effect on the copper fixation rate. However, at 50 °C, delayed drying resulted in a higher degree of copper fixation, while this effect was not observed at 22 °C. Post-treatment of ACQ treated wood with pressurized CO₂ immediately after treatment, reduced the pH of the solution in wood and resulted in rapid fixation of the copper. However, in time, the pH increased as CO₂ dissipated from the solution allowing the copper to re-solubilize.     

Effect of hot air post-treatments on copper leaching resistance in ACQ-D treated Chinese fir

Chinese fir (Cunninghamia lanceolata Hook.) wood cubes (19?×?19?×?19 mm³) were treated with amine copper quat-type D (ACQ-D) solution and fixed with different hot air post-treatments. The effects of temperature, relative humidity, duration, air circulation of post-treatment as well as the copper retention in the treated wood on copper leaching were investigated. With the help of ultraviolet or visible spectroscopy (UV/VIS), the valence conversion of copper in treated wood post-treated with optimal post-treatment conditions was investigated, and its relation with copper leaching was also discussed. The results showed that besides temperature and relative humidity, air circulation during hot air post-treatments also had a significant effect on accelerating copper fixation in ACQ-D treated wood. 70 °C, 80% R.H. with good air circulation provided a suitable condition for complete fixation of copper in a short period. After the applied post-treatments, up to 11.3% cupric copper reduced to cuprous form. A higher copper conversion rate usually corresponds to lower copper leaching, which is consistent with the contribution of lower water solubility cuprous copper.     

Preservative treatment of Douglas-fir lumber by the passive impregnation method with copper azole

Laser incised dry (mc=18%) and green (mc=33%) Douglas-fir was treated by the passive impregnation method of wood preservation having two different incising densities (7500 and 10000 holes/m²) and dipping times (3 and 12 hours). A 0.68% active ingredient solution of Copper Azole Type B (Tanalith CY) preservative was used in this study. The preservative retention and penetrated area were measured. The total preservative retention varied from 1.61 to 2.68 kg/m³ depending on the moisture content of wood and conditions of preservation, and in all cases it surpassed the minimum retention requirement for above ground use. The maximum penetrated area for dry lumber (mc=18%) was 96 and 88% across and along the grain, respectively. For green lumber (mc=33%), it was 90 and 85% across and along the grain, respectively.     

Kupfer-HDO—ein vielseitiger Wirkstoff im Holzschutz

Favourable toxic values of the water-insoluble effective substance Bis-(N-Cyclohexyldiazeniumdioxy)-copper, CU-HDO, for wood-destroying basidiomycetes and soft-rot resulted in the development of water-soluble, chromium-free wood preservative products. Biological tests of water-born formulations based on Cu-HDO showed threshold values after leaching, considerably lower than the values of conventional copper-/chromium-containing wood preservatives, especially for brown rot fungi. Examinations in application engineering with pine and spruce timbers indicated that penetration and distribution of the wood preservative come up to the requirements of an application in hazard class 4. Toxicological values and data on environmental aspects, especially concerning disposal of the impregnated wood, show that this formulation is an interesting alternative to wood preservatives based on conventional copper/chromium compounds.     

Relative leaching and aquatic toxicity of pressure-treated wood products using batch leaching tests

Size-reduced samples of southern yellow pine dimensional lumber, each treated with one of five different waterborne chemical preservatives, were leached using 18-h batch leaching tests. The wood preservatives included chromated copper arsenate (CCA), alkaline copper quaternary, copper boron azole, copper citrate, and copper dimethyldithiocarbamate. An unpreserved wood sample was tested as well. The batch leaching tests followed methodology prescribed in the U.S. Environmental Protection Agency toxicity characteristic leaching procedure (TCLP). The wood samples were first size-reduced and then leached using four different leaching solutions (synthetic landfill leachate, synthetic rainwater, deionized water, and synthetic seawater). CCA-treated wood leached greater concentrations of arsenic and copper relative to chromium, with copper leaching more with the TCLP and synthetic seawater. Copper leached at greater concentrations from the arsenic-free preservatives relative to CCA. Arsenic leached from CCA-treated wood at concentrations above the U.S. federal toxicity characteristic limit (5 mg/L). All of the arsenic-free alternatives displayed a greater degree of aquatic toxicity compared to CCA. Invertebrate and algal assays were more sensitive than Microtox. Examination of the relative leaching of the preservative compounds indicated that the arsenic-free preservatives were advantageous over CCA with respect to waste disposal and soil contamination issues but potentially posed a greater risk to aquatic ecosystems.     

Effect of fixation time on leaching of copper-ethanolamine based wood preservatives

Zusammenfassung Fixation in copper-ethanolamine treated Norway spruce wood is finished in the first or in the second week after impregnation depending on the concentration of wood preservatives used. However, copper losses increased after four weeks of fixation again, presumably due to lignin depolymerisation caused by ethanolamine.      

Effect of fixation time on leaching of copper-ethanolamine based wood preservatives

Fixation in copper-ethanolamine treated Norway spruce wood is finished in the first or in the second week after impregnation depending on the concentration of wood preservatives used. However, copper losses increased after four weeks of fixation again, presumably due to lignin depolymerisation caused by ethanolamine.     

Process related copper leaching during a combined wood preservation process

A combined wood impregnation process including impregnation with a chromium-free wood preservative and oil treatment was evaluated with regard to leaching of copper during the oil process. Two different experimental setups make up the balance of copper content in oil, wood samples and condensate water, also taking different fixation times and process durations into account. Copper is sufficiently fixed after 24 hours, and leaching of copper into the oil is low. Increasing the oil process time does not lead to increased leaching. The hot oil treatment of impregnated wood under vacuum atmosphere is a fast drying method without major negative consequences for the impregnated copper.     

Impact of surface water conditions on preservative leaching and aquatic toxicity from treated wood products

New alternative wood preservatives contain higher levels of copper (Cu) which can promote aquatic toxicity in natural water systems. Earlier work focused on evaluating toxicity using laboratory generated leaching solutions. In this study, the impact on preservative leaching and aquatic toxicity from treated wood products was evaluated using natural surface waters including waters from two rivers, three lakes, two wetlands, and one seawater, in addition to synthetic moderate hard water and deionized water. Blocks of wood treated with Cu based alternatives such as alkaline copper quaternary (ACQ) and copper boron azole (CBA), along with chromated copper arsenate (CCA)-treated wood, were leached under quiescent conditions, and total Cu, labile Cu, and heavy metal toxicity were measured. Results show that ACQ- and CBA-treated wood leach approximately 10 and 20 times more total Cu relative to CCA-treated wood and that the presence of organic and inorganic ligands in natural waters lowered the labile fraction of Cu relative to that from laboratory generated leaching solutions. Aquatic toxicity was found to correlate with the labile Cu fraction, and hence, the aquatic toxicity of the treated wood leachates was lower in natural waters in comparison to laboratory leaching solutions. The results of the present study suggest that studies designed to evaluate the impacts of treated wood should therefore consider the role of complexation in reducing the labile Cu fraction and its potential role in decreasing toxicity.     

An economical treatment schedule for boron impregnation of Eucalyptus grandis wood: Commercial trial of partially dried material

Being non-durable, Eucalyptus grandis wood needs treatment with preservative chemicals. As vacuum-pressure impregnation treatment being more suitable for commercial applications, and boron chemicals being environment-friendly for indoor uses, an economical treatment schedule (15 minutes initial vacuum of -85 kPa followed by a pressure of 1300 kPa for 15 minutes and a final vacuum of -85 kPa for 5 minutes) developed at the Kerala Forest Research Institute was tested for its commercial suitability for treating E. grandis wood with boron chemicals. A pooled mean dry salt retention (DSR) of 7.7 kg m ^-3 was achieved for wood in partially dried condition with average moisture content of around 32%, using a 6% boric acid equivalent (BAE) solution. This confirms the success of the schedule for commercial application, as the DSR achieved is much higher than the standard specification of many countries.     

Zur Prüfung und Bewertung der Umweltverträglichkeit von Holzschutzmitteln

Wood preservation can be made more environmentally compatible (1) by confining the use of wood preservative chemicals to the necessary minimum, and (2) by the use of effective and at the same time environmentally compatible wood preservatives. The aims and main points of testing and evaluating the environmental compatibility of wood preservatives are described. Crucial in this concern is the emission rate of the active ingredients of the wood preservatives (which leave the impregnated wood by leaching or evaporation), and this rate should be as low as possible for reasons of both long-term efficacy and low environmental load. The main pathways of possible environmental input of the active ingredients are leaching and evaporation during storage, transport and use of the impregnated wood and the input of their components or decomposition products during waste management. Looking at the leaching of non-fixing, not yet fixed as well as fixed wood preservative salts and organic active substances some problems arising in the practice of wood preservation and in the evaluation of the environmental compatibility of wood preservatives are dealt with and possible solutions are demonstrated.     

Fungal and termite resistance of wood treated with 4-methoxytrityl tetrafluoroborate

This study evaluates the decay and termite resistance of Scots pine (Pinus sylvestris L.) treated with 4-methoxytrityl tetrafluoroborate (MTFB). Decay resistance tests of unleached samples showed that 2%, 1.5% and 1% concentrations of MTFB (15.4 kg/m³, 11.1 kg/m³, and 7.4 kg/m³, retention levels, respectively) gave less than 2% decay of Postia placenta and concentrations of 2% and 1.5% less than 2% decay of Coniophora puteana. Wood specimens treated with 4-methoxytrityl tetrafluoroborate solutions were not protected against the brown rot fungi after a 14-day severe leaching process, suggesting excessive leaching of the chemical from wood. Treatment with 2% concentration protected against subterranean termites, Coptotermes formosanus Shiraki based on mass losses in both leached and unleached wood specimens in comparison with lower concentration levels. These results suggest that 4-methoxytrityl tetrafluoroborate might be promising to protect wood being used outdoors against termite attack. However, 4-methoxytrityl tetrafluoroborate did not protect wood against fungal decay. Field tests are needed to observe the performance of 4-methoxytrityl tetrafluoroborate treated wood in ground contact.     

Performance of wood impregnated with N-methylol and copper based aqueous solutions

The combination of copper and N-methylol compounds considerably improves the performance against copper sensitive fungi (G. trabeum and T. versicolor), while the fungicidal effect against copper tolerant strain (A. vaillantii) remained insufficient. Addition of N-methylol compounds to copper solution significantly reduces leaching from wood blocks impregnated with the solution of the lowest copper concentration (c_Cu =0.1%), and less notably reduces leaching from wood blocks impregnated with solutions of higher copper contents (c_Cu=0.5%).     

Performance of wood impregnated with N-methylol and copper based aqueous solutions

The combination of copper and N-methylol compounds considerably improves the performance against copper sensitive fungi (G. trabeum and T. versicolor), while the fungicidal effect against copper tolerant strain (A. vaillantii) remained insufficient. Addition of N-methylol compounds to copper solution significantly reduces leaching from wood blocks impregnated with the solution of the lowest copper concentration (c_Cu =0.1%), and less notably reduces leaching from wood blocks impregnated with solutions of higher copper contents (c_Cu=0.5%).     

Improvement of fungicidal properties and copper fixation of copper-ethanolamine wood preservatives using octanoic acid and boron compounds

Copper ethanolamine preservatives are one of the most important solutions for wood preservation. As copper itself can not ensure sufficient protection against wood destroying organisms we combine it with other co-biocides like quaternary ammonium compounds, azoles and/or boron. Influence of different boron compounds and octanoic acid on copper fixation as well as performance of spruce wood impregnated with different copper/ethanolamine/boron based aqueous solutions is described in this paper. Copper fixation was determined according to the modified ENV 1250 (1994) standard method, while performance against Antrodia vaillantii, Gloeophyllum trabeum and Trametes versicolor was tested according to the mini block procedure. The results showed that addition of boron increases copper leaching, but on the contrary improves performance against wood decay fungi. On the other hand, addition of octanoic acid improves copper fixation, and slightly decreases resistance against copper tolerant fungi.     

Modified QuEChERS Combination with Magnetic Solid-Phase Extraction for the Determination of 16 Preservatives by Gas Chromatography–Mass Spectrometry

In this paper, based on the mechanism of the quick, easy, cheap, effective, rugged and safe (QuEChERS) method, a novel graphene grafted silica-coated Fe₃O₄ (Fe₃O₄@SiO₂@G) was synthesized and applied as the efficient magnetic solid-phase extraction (MSPE) adsorbent for rapid cleanup of vegetable samples prior to analyzing 16 preservative residues by gas chromatography–mass spectrometry (GC-MS). The method, which took advantages of the novel nanoparticle adsorbent and an external magnetic field separation targets from samples, not only could avoid the time consuming of the traditional solid-phase extraction, but also could be developed for simultaneous determination of 16 preservative residues in vegetables. Various experimental parameters that could affect the extraction efficiencies have been investigated. Under the optimum conditions, 16 preservatives showed good linearity over the range of 0.02–2.00 mg/L and correlation coefficients (R ²) of 0.9946–0.9998. The limits of detections (LODs) were in the range of 0.21–11.50 μg/kg. The recoveries of 16 preservatives ranged from 78.3 to 116.7 %, and the relative standard deviations (RSDs) ranged from 1.4 to 11.9 %.     

Entsorgung von mit Holzschutzmitteln behandelten Hölzern

Recycling wood and industrial wood residues often contain various wood preservatives. The waste management for these residues can be recycling, deposition or combustion. Among the three possibilities combustion is the best way of usage. The combustion of wood residues containing organic or inorganic preservatives is influenced by the elementary composition of the preservative and the thermal and oxidative reaction pathes in the flame. Organic preservatives mostly can be thermally destructed by usual combustion conditions. Elevated combustion conditions are necessary for preservatives based on tar oils and chlorinated compounds. Among inorganic compounds, mercury and arsenic based preservatives have a considerable environmental impact. Other elements like copper, sinc, borine or chrome remain in ashes and cinders reducing the emmission problems towards an effective dust removal.     

Evaluation of new quaternary ammonium compound, didecyldimethylammonium tetrafluoroborate (DBF) in comparison with DDAC: Leachability and termite resistance tests

Modifications in the structure of wood preserving quaternary ammonium compounds (QACs) may result in improvements in leaching of components and biological resistance of treated wood. In this study, we evaluated the leaching characteristics and termite resistance of wood treated with a newly developed QAC compound didecyldimethylammonium tetrafluoroborate (DBF) in comparison with commercial DDAC, another QAC compound. Laboratory leaching tests showed that amount of DBF released from treated wood specimens was less than that of DDAC. However there was no difference between DBF and DDAC in the resistance of treated wood specimens against termite attack. Retention level at about 3 kg/m³ of DBF and DDAC seems to be enough to protect wood against termite attack, however, no comparative data are available for resistance of DBF and DDAC-treated wood against wood degrading fungi. Field tests are also needed to determine the performance of DBF-treated wood in ground contact in comparison with DDAC.     

Vorbehandlung von Fichtenholz mit Chemikalien mit dem Ziel der Verbesserung der Imprägnierbarkeit

Dried sprucewood (Picea abies L. Karst) is hardly penetrable with liquids, p.e. wood preservatives. The aim of this research was to improve the penetrability by means of pretreatments with chemicals. Small specimens (20×20×50 mm) were treated with different acids, alkali and chelating agents. Concentration, temperature and duration were varied. Subsequently, the specimens were impregnated with a water based preservative. The penetration and the retention of the liquid were determined. The pre-treatments with ammoniumoxalate, acetic acid and formic acid improved the penetrability slightly without attacking the wood structure. For further work with sawn planks, acetic acid, hexametaphosphate and oxalate were selected (see part 2).     

Effects of reduced levels of sulfite in wine production using mixtures with lysozyme and dimethyl dicarbonate on levels of volatile and biogenic amines

Sulphur dioxide (SO₂) is an important preservative for wine, but its presence in foods can cause allergies and this has given impetus to the research for alternatives. The aim of this study was to reduce levels of sulfite in wine production using mixtures with lysozyme and dimethyl dicarbonate and examine the influence on levels of volatile and biogenic amines. To do so, vinifications were carried out using lysozyme, dimethyl dicarbonate (DMDC) and mixtures of these with SO₂ in different concentrations (25 and 50 mg l^?1). Results were compared with a control vinification with only SO₂ (50 mg l^?1). Mixing low concentrations of SO₂ with lysozyme and DMDC reduced the concentration of biogenic amines (histamine, tyramine, putrescine, cadaverine, phenylethylamine + spermidine and spermine). In general, the total concentration of volatile amines (dimethylamine, isopropylamine, isobutylamine, pyrrolidine, ethylamine, diethylamine, amylamine and hexylamine) was higher in the sample fermented only with SO₂. The concentrations of amines with secondary amino groups (dimethylamine, diethylamine, pyrrolidine) were higher in the sample only fermented with SO₂ than those fermented with DMDC and lysozyme or with a mixture of preservatives. When SO₂ was the only preservative in wine, total amine concentration (biogenic and volatile amines) was higher than for the rest of the treatments. Lysozyme by itself, and lysozyme mixed with SO₂, both reduced the formation of biogenic amines but given the antioxidant activity of SO₂ the use of the preservative mixture seems more advisable.