Method development for the determination of wood preservatives in commercially treated wood using gas chromatography-mass spectrometry

Fungicides and insecticides are commonly used preservatives to protect wood products against microbiological degradations. Currently, there is a lack of analytical methods addressing the quantitative determination of a wide range of wood preserving species in wood matrices. In this study, a reliable method was developed for the determination of a mixture of wood preserving agents with differing chemical structures (i.e., properties), including tebuconazole (TAZ), propiconazole (PAZ), 3-iodo-2-propynyl butylcarbamate (IPBC), and permethrin (PER), in pine wood. The analyte recoveries obtained by Soxhlet and multiple-stage sonication extractions were compared. While both extraction methods yielded similar results (80–100%), Soxhlet extraction was found to be less labor-intensive and thus preferred providing also lower RSDs of 1–6%. In comparison to methanol, commonly used as an extraction solvent for triazoles, acetone yielded similar extraction efficiencies for all analytes while reducing the time of sample concentration. The solid phase extraction method for triazoles was adapted to allow for a separation of IPBC and PER from the wood matrix. As opposed to previous studies, three recovery standards were employed, which enabled the correction of individual analyte losses during the sample preparation. The matrix-affected limits of detection (LODs) using gas chromatography with mass spectrometric detection were nearly the same for triazoles 0.07 and 0.21 ng g⁻¹ for PAZ and TAZ in sapwood and 0.18 and 0.21 ng g⁻¹ in heartwood, respectively. Higher LODs were observed for IPBC and PER: 3.9 and 1.7 ng g⁻¹ in sapwood, and 2.0 and 6.0 ng g⁻¹ in heartwood, respectively. The recoveries in the wood submitted to commercial sample treatment showed gradient distribution of analytes depending on the penetration of the treatment.     

Potential of solid phase microextraction and gas chromatography for quarantine-required detection of wood packaging in shipping containers

Solid phase microextraction (SPME) coupled with gas chromatography (GC) was used to detect terpene hydrocarbons inside shipping containers entering New Zealand. The utility of this system for the rapid detection of undeclared wood packaging for quarantine purposes was demonstrated. A portable dynamic air-sampling device was built to house a SPME fibre and allow the air from shipping containers to be sampled. The effects of sample flow rate and sampling time were investigated and sampling conditions of 100 mL/min for 30 s were chosen to keep sampling within the linear range. A CV of less than 15% (n = 12) was obtained for all the compounds analysed under these conditions. To obtain an estimate for the limit of detection (LOD) for the terpene hydrocarbons of interest, small quantities of lime oil were placed in an empty shipping container and the air inside was analysed. LOD (S/N = 3) was estimated to be in the order of 50-100 ng/L of air using GC with flame ionisation detection (GC-FID). Finally, the device was tested in fully laden containers and was shown to be effective for trapping terpene hydrocarbons indicative of wood packaging.     

Thermoplasticization of wood. I. Benzylation of wood

A study of converting wood into thermoplastic materials was undertaken to develop a new technique in effective utilization of wood wastes. Thermoplasticizatoin of wood carried out by means benzylation. Various reaction parameters, such as alkalinity of reaction media, reaction temperature, and time were taken into account to produce benzylated wood with different degrees of substitution (based on weight gain) FTIR, DSC, DMTA, SEM and x-ray crystallography were used to characterize the chemical and mechanical properties of benzylated wood. Experimental data showed that preswelling and reaction temperature had critical effects on benzylation reaction. Lignin in wood appeared to inhibit benzylation but extractives had little effect. Different species showed some variation in reaction rates. The thermoplasticized wood exhibited good melting properties and were readily molded into bulk materials or extruded into films and sheets. A wide range of glass transition temperatures from 66 to 280°C for the benezylatedwoods was achieved, and they were larely dependent on the weight gain. The molded and extruded products exhibited acceptable mechanical strength for structural engineering applications. The property and structure relationship for the thermoplasticized wood were discussed     

木材热塑化

利用适当的化学改性反应特别是经典的纤维索改性反应如酯化、醚化反应对木材进行化学改性，可使木材转化为可熔、可溶的新型热塑性高分子材料。这种热塑性木材可用普通塑料加工成型的方法进行加工，制造出许多新产品。为扩大木材的加工方法、劣废木材资源更有效的综合利用及提高木材的应用价值开辟了新的途径。放已成为近十年来木材综合利用新技术研究开发的新热点之一。本文综述这一研究领域的现状。     

Determination of the alkyl- and methoxy-phenolic content in wood extractives by micellar solid-phase microextraction and gas chromatography-mass spectrometry

This work combines the utilization of the micellar media during the extraction step and the focused microwave-assisted extraction followed by the solid-phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS) to determine the alkyl- and methoxy-phenolic content in wood extractives. The proposed environmental-friendly method is mainly characterized by short analysis times (5 min for the microwaves extraction step) and for avoiding the use of organic solvents. Different surfactants were tried for the extraction process: the cationic surfactant CTAB and the non-ionic surfactants Triton X-100 and POLE, with similar extraction efficiencies (85.5-99.7%). The overall method presents limits of detection in the ng g⁻¹ region for the alkylphenols (from 7 to 150 ng g⁻¹) and in the μg g⁻¹ region for the methoxyphenols (from 0.80 to 22.9 μg g⁻¹). The vanillin was the compound most abundant in the wood extractives studied, with concentrations up to 116.2 mg kg⁻¹.     

Characterization of victorian soft brown coal wood by microscopic techniques and Curie-Point pyrolysis combined with gas chromatography-mass spectrometry

Pyrolysis combined with gas chromatography-mass spectrometry is used in an attempt to distinguish lignins derived from an angiosperm and a gymnosperm on the basis of their pyrolysis products. The study is extended to examine the pyrolysis products of Australian soft brown coal woods that have undergone varying degrees of gelification during the soft brown coal stage of coalification. Comparison of the lignin and brown coal pyrograms shows that the brown coals may be derived from gymnosperms, which is in agreement with the results of previous microscopic studies. Poorly gelified brown coals are also shown to contain significant amounts of furan-type products which are not present in the gelified soft brown coal woods. No systematic variation was observed in the distribution of methoxy compounds and the macroscopically and microscopically defined degree of gelification. Finally pyrolysis of low rank vitrinites shows a relative lack of substituted phenols in their pyrograms, but a relative increase in concentration of substituted polycyclic aromatics, compared with highly gelified brown coals.     

Studies in organic archaeometry VII--differentiation of wood and bark pitches by pyrolysis capillary gas chromatography (PY-CGC)

Tars and pitches were prepared from wood and bark of various deciduous trees and conifers and analysed with the intention to distinguish between various starting materials. All this was done before the background of an archaeometrical problem: to provide a basis for the chemical identification of those pitches which are frequently found in archaeological excavations. Intending to extend the already existing possibilities for such analyses the present paper is dealing with the application of pyrolysis coupled with capillary gas chromatography and by subsequent chemometric studies. It could be shown that by this technique indeed not only tars and pitches prepared from deciduous trees and from conifers could clearly be differentiated, but that even respective species could be identified. Thus a fundament is provided for future studies aiming to identify the starting material of real archaeological finds by a novel method which requires by far less quantities of sample material as compared to the methods hitherto used by us.     

Qualitative mass spectrometric analysis of the volatile fraction of creosote-treated railway wood sleepers by using comprehensive two-dimensional gas chromatography

The volatile composition of 20-year-old out-of-service creosote-treated railway wood sleepers was studied. The emitted volatile fraction was collected by means of dynamic purge-and-trap concentration at ambient temperature, and analyzed by comprehensive two-dimensional gas chromatography (GC x GC) hyphenated with mass spectrometric detection systems, using quadrupole (GC x GC/qMS) and time-of-flight (GC x GC/ToF-MS) mass analyzers and selective nitrogen-phosphorus detection (GC x GC-NPD). The analysis of mass spectrometry data and GC x GC retention time allowed the tentative identification of about 300 compounds based on spectrometric data and positioning of each compound in the GC x GC plot. Major important headspace components are polyaromatic hydrocarbons, phenols and benzene derivatives, hydrocarbons and heterocyclic compounds containing nitrogen, sulphur or oxygen atoms. Many of the reported compounds are listed as belonging to toxicological substance classes which have been related to harmful health effects. GC x GC provides greater speciation and evidence of composition heterogenicity of the sample than one-dimensional GC analysis, thus allowing to better demonstrate its potential toxicity. Data obtained by specific detection systems for N-heterocycles assisted mass data interpretation assignments. The enhanced separation power obtained after GC x GC compared to one-dimensional gas chromatography (1D-GC) together with spectral deconvolution and correlation with physical-chemical data, allowed the identification of complex isomer clusters, as demonstrated for alkylquinolines, and applied also to alkylphenols, alkylbenzenes and alkylnaphthalenes.     

Determination of organic compounds from wood combustion aerosol nanoparticles by different gas chromatographic systems and by aerosol mass spectrometry

Organic compounds in atmospheric nanoparticles have an effect on human health and the climate. The determination of these particles is challenged by the difficulty of sampling, the complexity of sample composition, and the trace-level concentrations of the compounds. Meeting the challenge requires the development of sophisticated sampling systems for size-resolved particles and the optimization of sensitive, accurate and simple analytical techniques and methods. A new sampling system is proposed where particles are charged with a bipolar charger and size-segregated with a differential mobility analyzer. This system was successfully used to sample particles from wood pyrolysis with particle sizes 30–100 nm. Particles were analyzed by four techniques: comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry, gas chromatography–time-of-flight mass spectrometry, gas chromatography–quadrupole mass spectrometry, and aerosol mass spectrometry (aerosol MS). In the chromatographic techniques, particles were collected on a filter and analyzed off-line after sample preparation, whereas in the aerosol MS, particle analysis was performed directly from the particle source. Target compounds of the samples were polyaromatic hydrocarbons and n-alkanes. The analytical techniques were compared and their advantages and disadvantages were evaluated. The sampling system operated well and target compounds were identified in low concentrations.     

Determination of naturally occurring formaldehyde levels in sap and wood tissue of maple trees using gas chromatgraphy/mass spectrometry

The occurrence of formaldehyde in sap and wood tissue of treated and untreated maple sugar trees was investigated using GC/MS. Samples were collected at different periods of the 2009 season and at different locations in Quebec, Canada. The natural concentration of formaldehyde found in untreated samples varied according to periods and locations and ranged from below the LOQ to 1.82 mg/kg for sap samples and from 2.39 to 8.92 mg/kg of fresh tissue for wood samples. Late season samples tended to have higher concentrations of formaldehyde. Samples of sap and wood tissue from tapholes treated with solutions of formaldehyde showed increased concentrations of formaldehyde for many days after treatment and were clearly distinct from untreated samples. These results will be useful to elaborate new inspection procedures for sugarbushes to control the illegal use of formaldehyde.     

Effect of thermal-treatment of wood fibres on properties of flat-pressed wood plastic composites

This study aimed to enhance the dimensional stability of flat-pressed wood plastic composites (WPCs) containing fast growing wood fibres by a thermal-treatment method. The wood fibres were treated at three different temperatures (120, 150, or 180 °C) for 20 or 40 min in a laboratory autoclave. The WPC panels were made from dry-blended Eucalyptus camaldulensis wood fibres and polypropylene (PP) powder (50:50 by weight) using a conventional flat-press process under laboratory conditions. Thickness swelling and water absorption of the WPC panels significantly decreased with increasing the treatment temperature and time. The thermal-treatment of eucalyptus wood fibres slightly decreased the screw withdrawal resistance of the WPC panels as compared to the reference panels while the flexural properties and internal bond strength were more seriously affected by the treatment. The present study revealed that the thermal-treatment of the wood fibres significantly improved the dimensional stability of the WPC panels.     

Identification of a novel series of alkylitaconic acids in wood cultures of Ceriporiopsis subvermispora by gas chromatography/mass spectrometry.

A novel series of long-chain unsaturated dicarboxylic acids consisting of a long aliphatic chain attached to the C-3 position of itaconic acid has been identified by gas chromatography/mass spectrometry during in vitro decay of eucalypt wood by the white-rot basidiomycete Ceriporiopsis subvermispora. The major compounds were identified as tetradecyl-, 7-hexadecenyl- and hexadecylitaconic acids by their mass fragmentation patterns. Other members of the same compound series, identified as dodecanyl-, tridecanyl-, tetradecenyl-, pentadecanyl-, octadecenyl- and octadecanylitaconic acids, were present in very minor amounts or traces. Whereas hexadecenylitaconic acid has already been reported in cultures of C. subvermispora, to our knowledge this is the first report of the presence of the other alkylitaconic acids in fungal cultures. These new alkylitaconic-type metabolites may constitute a source for peroxidizable lipids involved in lignin degradation during wood decay by C. subvermispora and other white-rot basidiomycetes.     

The effect of wood extractives on the thermal stability of different wood species

This study compares the thermal stability of different wood species, which is an important factor for the production of wood–polymer composites (WPCs), and investigates the effect of extraction on thermal properties. The chemical composition of four wood species – Quercus alba, Pinus radiata, Eucalyptus grandis and Acacia cyclops – has been determined, as the species is expected to affect the thermal stability of wood. Subsequently, the hot-water (HW) extractives, ethanol/cyclohexane (E/C) extractives and both extractives were eliminated from the wood via Soxhlet extraction and the thermal stability of the wood determined with thermogravimetric analysis (TGA) under identical conditions. The results suggest that a higher cellulose and lignin content leads to better thermal stability of wood in different temperature regimes. In all cases, the removal of extractives improved the thermal stability of the wood. The effect of combined extractions was more pronounced than of an individual extraction and E/C-extraction caused less improvement in the thermal stability of wood than HW extraction. The degradation of the investigated wood extractives occurred at low rates over a broad temperature range. Pure cellulose exhibited superior thermal stability compared to wood, but differences were observed between the investigated wood species.     

Application of gas chromatography - field asymmetric ion mobility spectrometry (GC-FAIMS) for the detection of organic preservatives in wood

The purpose of the investigations reported was a feasibility study of field asymmetric ion mobility spectrometry (FAIMS) applications for the characterization of recovered wood. Especially the treatment with organic wood preservatives represented by their active substances should be detected in concentrations commonly used for timber products. The following pesticides were determined: PCP, lindane, dichlofluanide, tolylfluanide, propiconazole, tebuconazole, IPBC (iodine-propyl-butyl-carbamate), K-HDO ((N-Cyclohexyl-diazeniumdioxy)-potassium) and fenoxycarb. The first step was to show that such compounds can be vaporized under moderate conditions. Solid-phase microextraction (SPME) was capable for sampling and enrichment. The reference analytics was made by gas chromatography coupled with mass spectrometry (GC-MS). Both, waste wood, in this case window frames from reconstruction work, and self-prepared doped wood samples were utilized. For analyzing the complex mixture of vaporized native and artificial ingredients of the lignocellulose material a chromatographic pre-separation was necessary. Hence, the second step was to study the behavior of active substances in the analysis with GC-FAIMS to clarify which peaks in positive and negative mode are dedicated to wood preservatives. At least one strong signal from every selected active compound was located for clear identification. With that knowledge, FAIMS was successfully applied for the distinction of natural and treated wood samples. The discrimination can be a basis for industrial sorting plants which could help to increase the contemporary amount of material usage of recovered wood for a more ecological and economical handling of natural resources.     

Biochemical analysis of wood and wood products by pyrolysis-mass spectrometry and multivariate analysis

Pyrolysis—mass spectrometry in combination with discriminant analysis and a newly development non-supervised mixture analysis approach is shown to provide valuable information about the biochemical composition of wood and wood products. The application of this technique to the chemotaxonomy of sagebrush (Artemisia) species as well as to the quality control of wood pulping processes is discussed. With regard to the latter application strong correlations are found between classical lignin and xylan determinations and direct pyrolysis—mass spectrometric analysis results.     

Thermogravimetric analysis of wood, holocellulose, and lignin from five wood species

Thermogravimetry has been widely applied to the study of wood and cellulose materials. There is a general agreement that decomposition of hemicellulose, cellulose, and ligning take place in a relatively narrow range of temperature, partially overlapping. There is no a definitive demonstration of which thermal feature corresponds to each component. In this study, three hardwood and two softwood species were considered: Castannea sativa, Eucaliptus globulus, Quercus robur, Pinus pinaster, and Pinus sylvestris. Thermogravimetric analysis of wood powder, ethanol-extracted wood, holocellulose, and lignin, obtained from those species revealed some important differences between hardwood and softwood holocelluloses and an important role of the ethanol-extractives, which explain the different behavior observed in both kinds of wood. FTIR spectra obtained from the evolved gases helped to clarify some degradation steps.     

A rapid pyrolytical method for the determination of wood preservatives in treated wood

Analytical laboratories are often confronted with the question whether a board of wood has been treated with an insecticide or fungicide or not at all. Generally this question is difficult to answer in the case of organic wood preservatives and requires considerable time for analytical procedures. Therefore, a simple and rapid method for determining the most common organic wood preservatives in a one-step procedure has been developed. They were measured by gas chromatography after thermal treatment by a Curie-point pyrolyser, directly attached to the GC. Under these conditions the specific compounds tended to be predominatly vaporised rather than pyrolysed. For analysis, a mass-selective detector (MSD) was used in selected ion mode (SIM). In one analytical step, up to eight different preservatives can be identified. Detection limits were in the range between 0.01 and 0.7 g/m².     

The effect of chemical modification on the strength of wood and bonded wood joints

The effect of propionic, crotonic or methacrylic anhydride (MA) modification on the lab joint strength of monomer bonded veneer strips was investigated. Lap joints were formed by hot pressing veneers of modified wood with monomer in the presence of free radical initiator and bond strength was determined on an Automatic Bonding Evaluation System tensile tester. Test results indicated that chemical treatment improved bond quality between hydrophilic wood and hydrophobic monomer. Extremely strong bonds (wet and dry conditions) formed in the case of MA modified veneer strips. In addition, the effect of chemical modification on the mechanical properties of strips was also investigated. Chemical modification had a detrimental effect on the mechanical properties.     

Influence of wood mercerization on the crystallization of polypropylene in wood/PP composites

Mercerization process is very significant because the alkali treatment facilitates reactivity of lignocellulosic fillers, thus allowing better response to chemical modification. In the present study, the effect of mercerization of pine wood on the nucleation ability of polypropylene was investigated by means of differential scanning calorimetry. We discovered that for the composites with wood containing cellulose II, the decrease in the crystal conversion of the polymer matrix and increase in the half-time of crystallization values are significant. It can be concluded that the amount of cellulose II formed upon alkalization of lignocellulosic fillers determines their nucleation ability. To evaluate the transcrystalline effects caused by various woods, which were untreated or treated with sodium hydroxide, the polarized optical microscopy was also performed. The nucleation of polypropylene on the surface of wood was investigated by induction time measurement. It was found that surfaces of the unmodified wood generate epitaxial nucleation, whereas the mercerized wood generates nonepitaxial nucleation. The differences in the type of nucleation suggest that the effectiveness of formation of transcrystalline structures depends on the contribution of cellulose I and cellulose II. Moreover, the presence of epitaxy is not necessary for the appearance of transcrystalline structures. The results showed that the transcrystalline structures appeared in each system, even with wood containing significant contribution of cellulose II. The only difference noted was the change in the nucleation abilities of the wood surface. Results of this study imply the necessity of quantitative determination of the contributions of cellulose I and cellulose II, whose presence determine the type of nucleation and nucleation ability of the filler surface.