Effects of Fire Suppression Agents and Weathering in the Analysis of Fire Debris by HS-MS eNose.

In arson attacks the detection of ignitable liquid residues (ILRs) at fire scenes provides key evidence since ignitable liquids, such as gasoline, are commonly used to initiate the fire. In most forensic laboratories gas chromatography-mass spectrometry is employed for the analysis of ILRs. When a fire occurs, suppression agents are used to extinguish the fire and, before the scene is investigated, the samples at the scene are subjected to a variety of processes such as weathering, which can significantly modify the chemical composition and thus lead to erroneous conclusions. In order to avoid this possibility, the application of chemometric tools that help the analyst to extract useful information from data is very advantageous. The study described here concerned the application of a headspace-mass spectrometry electronic nose (HS-MS eNose) combined with chemometric tools to determine the presence/absence of gasoline in weathered fire debris samples. The effect of applying two suppression agents (Cafoam Aquafoam AF-6 and Pyro-chem PK-80 Powder) and delays in the sampling time (from 0 to 48 h) were studied. It was found that, although the suppression systems affect the mass spectra, the HS-MS eNose in combination with suitable pattern recognition chemometric tools, such as linear discriminant analysis, is able to identify the presence of gasoline in any of the studied situations (100% correct classification).

Release of terpenes from fir wood during its long-term use and in thermal treatment.

Building structures made from fir wood are often attacked by wood-destroying insects for which the terpenes it contains serve as attractants. One of the possibilities for extending the lifetime of structures is to use older wood with a lower content of terpenes and/or thermally modified wood. The study evaluated the levels of terpenes in naturally aged fir wood (108, 146, 279, 287 and 390 years) and their decrease by thermal treatment (the temperature of 60 °C and 120 °C, treatment duration of 10 h). Terpenes were extracted from wood samples by hexane and analyzed by gas-chromatography mass-spectrometry (GC-MS). The results indicate that recent fir wood contained approximately 60 times more terpenes than the oldest wood (186:3.1 mg/kg). The thermal wood treatment speeded up the release of terpenes. The temperature of 60 °C caused a loss in terpenes in the recent fir wood by 62%, the temperature of 120 °C even by >99%. After the treatment at the temperature of 60 °C the recent fir wood had approximately the same quantity of terpenes as non-thermally treated 108 year old wood, i.e., approximately 60-70 mg/kg. After the thermal treatment at the temperature of 120 °C the quantity of terpenes dropped in the recent as well as the old fir wood to minimum quantities (0.7-1.1 mg/kg). The thermal treatment can thus be used as a suitable method for the protection of fir wood from wood-destroying insects.

Changes of Meranti, Padauk, and Merbau Wood Lignin during the ThermoWood Process.

Thermal modification is an environmentally friendly process in which technological properties of wood are modified using thermal energy without adding chemicals, the result of which is a value-added product. Wood samples of three tropical wood species (meranti, padauk, and merbau) were thermally treated according to the ThermoWood process at various temperatures (160, 180, 210 °C) and changes in isolated lignin were evaluated by nitrobenzene oxidation (NBO), Fourier-transform infrared spectroscopy (FTIR), and size exclusion chromatography (SEC). New data on the lignins of the investigated wood species were obtained, e.g., syringyl to guaiacyl ratio values (S/G) were 1.21, 1.70, and 3.09, and molecular weights were approx. 8600, 4300, and 8300 g·mol-1 for meranti, padauk, and merbau, respectively. Higher temperatures cause a decrease of methoxyls and an increase in C=O groups. Simultaneous degradation and condensation reactions in lignin occur during thermal treatment, the latter prevailing at higher temperatures.

The Effect of Heat Flux to the Fire-Technical and Chemical Properties of Spruce Wood (Picea abies L.).

The paper assesses the influence of the heat flux on spruce wood (Picea abies L.) behavior. The heat flux was performed at 15, 20, 25, and 30 kW·m-2. The fire-technical properties, such as the mass burning rate, charring thickness, charring rate, as well as the chemical composition (contents of the extractives, lignin, cellulose, holocellulose), of wood were determined. The highest burning rate of spruce wood of 0.32%·s-1 was reached at the heat flux of 30 kW·m-2. The charring rate ranged from 1.004 mm·min-1 (15 kW·m-2) to 2.016 mm·min-1 (30 kW·m-2). The proposed model of the charring process of spruce wood in time and appropriate thickness as a selected parameter is applicable in validation of the results of computer fire models in the design of fire protection of wooden buildings. The decrease in the holocellulose content mostly caused by the degradation of hemicelluloses was observed during thermal loading. The biggest decrease in hemicelluloses (24.94%) was recorded in samples loaded at 30 kW·m-2. The contents of cellulose increased due to the structural changes (carbonization and crosslinking), the content of lignin increased as well due to its higher thermal stability compared to saccharides, as well as the resulting lignin condensation.

Effect of Natural Aging on Oak Wood Fire Resistance.

The paper deals with the assessment of the age of oak wood (0, 10, 40, 80 and 120 years) on its fire resistance. Chemical composition of wood (extractives, cellulose, holocellulose, lignin) was determined by wet chemistry methods and elementary analysis was performed according to ISO standards. From the fire-technical properties, the flame ignition and the spontaneous ignition temperature (including calculated activation energy) and mass burning rate were evaluated. The lignin content does not change, the content of extractives and cellulose is higher and the content of holocellulose decreases with the higher age of wood. The elementary analysis shows the lowest proportion content of nitrogen, sulfur, phosphor and the highest content of carbon in the oldest wood. Values of flame ignition and spontaneous ignition temperature for individual samples were very similar. The activation energy ranged from 42.4 kJ·mol-1 (120-year-old) to 50.7 kJ·mol-1 (40-year-old), and the burning rate varied from 0.2992%·s-1 (80-year-old) to 0.4965%·s-1 (10-year-old). The difference among the values of spontaneous ignition activation energy is clear evidence of higher resistance to initiation of older wood (40- and 80-year-old) in comparison with the younger oak wood (0- and 10-year-old). The oldest sample is the least thermally resistant due to the different chemical composition compared to the younger wood.

The Influence of Nanoparticles on Fire Retardancy of Pedunculate Oak Wood.

Traditional flame retardants often contain halogens and produce toxic gases when burned. Hence, in this study, low-cost, environmentally friendly compounds that act as fire retardants are investigated. These materials often contain nanoparticles, from which TiO2 and SiO2 are the most promising. In this work, pedunculate oak wood specimens were modified with sodium silicate (Na2SiO3, i.e., water glass) and TiO2, SiO2, and ZnO nanoparticles using the vacuum-pressure technique. Changes in the samples and fire characteristics of modified wood were studied via thermal analysis (TA), infrared spectroscopy (FTIR), and scanning electron microscopy, coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). The results of TA showed the most significant wood decomposition at a temperature of 350 °C, with a non-significant influence of the nanoparticles. A dominant effect of sodium silicate was observed in the main weight-loss step, resulting in a drop in decomposition temperature within the temperature range of 36-44 °C. More intensive decomposition of wood treated with water glass and nanoparticles led to a faster release of non-combustible gases, which slowed down the combustion process. The results demonstrated that wood modifications using sodium silicate and nanoparticle systems have potentially enhanced flame retardant properties.

Flammability Characteristics of Thermally Modified Meranti Wood Treated with Natural and Synthetic Fire Retardants.

This paper deals with the effect of synthetic and natural flame retardants on flammability characteristics and chemical changes in thermally treated meranti wood (Shorea spp.). The basic chemical composition (extractives, lignin, holocellulose, cellulose, and hemicelluloses) was evaluated to clarify the relationships of temperature modifications (160 °C, 180 °C, and 210 °C) and incineration for 600 s. Weight loss, burning speed, the maximum burning rate, and the time to reach the maximum burning rate were evaluated. Relationships between flammable properties and chemical changes in thermally modified wood were evaluated with the Spearman correlation. The thermal modification did not confirm a positive contribution to the flammability and combustion properties of meranti wood. The effect of the synthetic retardant on all combustion properties was significantly higher compared to that of the natural retardant.

Structural Changes of Oak Wood Main Components Caused by Thermal Modification.

Thermal modification of wood causes chemical changes that significantly affect the physical, mechanical and biological properties of wood; thus, it is essential to investigate these changes for better utilization of products. Fourier transform infrared spectroscopy and size exclusion chromatography were used for evaluation of chemical changes at thermal treatment of oak wood. Thermal modification was applied according to Thermowood process at the temperatures of 160, 180 and 210 °C, respectively. The results showed that hemicelluloses are less thermally stable than cellulose. Chains of polysaccharides split to shorter ones leading to a decrease of the degree of polymerization and an increase of polydispersity. At the highest temperature of the treatment (210 °C), also crosslinking reactions take place. At lower temperatures degradation reactions of lignin predominate, higher temperatures cause mainly condensation reactions and a molecular weight increase. Chemical changes in main components of thermally modified wood mainly affect its mechanical properties, which should be considered into account especially when designing various timber constructions.

Chemical alterations of pine wood saccharides during heat sterilisation.

Alterations in saccharides during heat sterilisation of pine wood (Pinus sylvestris L.) were investigated. The mass loss, extractives, lignin, cellulose, holocellulose and hemicelluloses were determined. Changes in saccharides were evaluated by the determination of monosaccharides in wood, size exclusion chromatography (SEC) as well as Fourier transform infrared (FTIR) spectroscopy. During heat sterilisation of pine wood the slight mass loss, an increase in extractives and a decrease in lignin and polysaccharides were observed. Hemicelluloses are degraded approximately twice as fast as cellulose. The degree of polymerisation of cellulose decreases approximately by 10% and it increases in holocellulose (by approx. 8%) as a result of a faster degradation of shorter hemicellulose chains. FTIR spectroscopy shows that sterilisation results in the deacetylation of cellulose and the formation of new carbonyl groups, an increase in the total crystallinity index (TCI) and a decrease in the lateral order index (LOI) and the hydrogen-bond intensity (HBI).

Effects of thermal treatment on chemical, mechanical and colour traits in Norway spruce wood.

In several different branches of the wood industry heat treatment is a growing application as it changes the chemical, mechanical, physical and biological properties of wood. Investigations using wet chemical analyses, Fourier transform infrared spectroscopy, size exclusion chromatography, and CIELab colour system have been conducted to study the changes in Norway spruce wood subjected to temperature up to 270°C over a 30 min time period. The results showed that mass loss (ML), total crystallinity index (TCI) of cellulose, total colour difference (ΔE*), and the content of lignin and extractives increased with the temperature, whereas degree of polymerization (DP) of cellulose, modulus of rupture (MOR), modulus of elasticity (MOE), lightness difference (ΔL*), and the content of holocellulose, cellulose and hemicelluloses all decreased with the thermal treatment. Relationships between temperature and the examined wood traits were all fitted by exponential curves. Power law relationships were found to fit the trends for DP of cellulose with ΔE*, ΔL*, and TCI of cellulose. Also found were power law regressions for the content of hemicelluloses with MOE, MOR, ΔL*, and ML. Temperatures ranging from 20 to 187°C formed a compact cluster, clearly separated from the higher examined temperatures in the multivariate wood trait space.