Concentrations Of Resin Acids Research Articles

Making wood inspection easier: FTIR spectroscopy and machine learning for Brazilian native commercial wood species identification.

The molecular structure of wood is mainly based on cellulose, lignin, and hemicellulose. However, low concentrations of lipids, phenolic compounds, terpenoids, fatty acids, resin acids, and waxes can also be found. In general, their color, smell, texture, quantity, and distribution of pores are used in human sensory analysis to identify native wood species, which may lead to erroneous classification, impairing quality control and inspection of commercialized wood. This study developed a fast and accurate method to discriminate Brazilian native commercial wood species using Fourier Transform Infrared Spectroscopy (FTIR) and machine learning algorithms. It not only solves the limitations of traditional methods but also goes beyond as it allows fast analyses to be obtained at low cost and high accuracy. In this work, we provide the identification of five Brazilian native wood species: Angelim-pedra (Hymenolobium petraeum Ducke), Cambara (Gochnatia polymorpha), Cedrinho (Erisma uncinatum), Champagne (Dipteryx odorata), and Peroba do Norte (Goupia glabra Aubl). The results showed the great potential of FTIR and multivariate analysis for wood sample classification; here, the Linear SVM differentiated the five wood species with an accuracy of 98%. The developed method allows industries, laboratories, companies, and control bodies to identify the nature of the wood product after being extracted and semi-manufactured.

Effect of ferrate pretreatment on anaerobic digestibility of primary sludge spiked with resin acids.

Resin acids are mixtures of high molecular weight carboxylic acids found in tree resins. Due to higher hydrophobicity and low solubility, they tend to adsorb on the suspended solids in pulp and paper (P&P) mill wastewater and accumulate in primary sludge through settling. Anaerobic digestion (AD) is a common practice stabilizing sludge; however, high concentration of resin acids affects the AD process. The aim of this research was mainly to determine the impact of ferrate (Fe (VI)) oxidation on selected resin acids and anaerobic digestibility of ferrate-treated primary sludge (PS) spiked with the resin acids. First, batch control oxidation of model resin acids with Fe (VI) was conducted to identify an optimum dosage, pH and contact time using a Box-Behnken design approach. Thereafter, anaerobic treatability studies of primary sludge spiked with resin acids both under control condition and optimum ferrate pretreatment were conducted. Up to 97% oxidation of resin acids occurred in pure water, while only 44%-62% oxidation of resin acids occurred in PS with an increasing Fe (VI) dosage from 0.034 to 0.137mg Fe (VI)/mg tCODfed. The pretreatment did not affect the anaerobic biodegradability of resin acids; however, it lowered their negative influences on the PS digestibility. About 0.076mg Fe (VI) dosage/mg tCODfed solubilized the sludge increasing the methane production by 40% compared to the untreated digester. The potential benefits of ferrate pretreatment of P&P primary sludge include resin acids oxidation and subsequent toxicity reduction, higher sludge solubilization enhancing methane production and enabling anaerobic digestion at higher COD loading.

Synthesis of polyoxymethylene dimethyl ethers from formaldehyde and dimethoxymethane by the coupling of extraction and catalytic reaction

The coupling of catalysis and extraction for the synthesis of polyoxymethylene dimethyl ethers (PODEn) was investigated from low-cost formaldehyde (FA) and dimethoxymethane (DMM). The process used sulfonic acid resins as catalysts and suitable organic solvents as the extractant. The effects of resin acidity, acid content, and pore structure on the catalytic performance were investigated. The correlation between the partition coefficient of FA and catalytic activity for preparation of PODEn was studied. It was found that the yield of PODE3-8 was significantly higher than that without the use of extractant. Dimethoxymethane (EDC) exhibited the highest performance. The effect of various factors on the catalytic reaction, such as the amount of catalyst, the molar ratio of FA to DMM, reaction temperature, reaction time and the types and dosage of different extractants, were explored. Under the optimal conditions of nFA:nDMM = 2:1, 80 °C, 4 wt% D002 catalyst, vEDC:DMM+FA = 1:1 and 8 h, the PODE3-8 yield enhanced from 6.12% to 55.86%.

Trace analysis of resin acids in surface waters by direct injection liquid chromatography time of flight mass spectrometry and triple quadrupole mass spectrometry

A rapid and sensitive liquid chromatography (LC) quadrupole time of flight (QTOF) method has been developed for the determination of resin acid concentrations in aqueous pulp and paper effluent related samples. Calibration R2 of ≥0.995 for twelve resin acids, namely dehydroabietic, 8(14)-abietenic, dihydroisopimaric, levopimaric, neoabietic, pimaric, sandaracopimaric, abietic, isopimaric, palustric, chlorodehydroabietic, and dichlorodehydroabietic acids, was demonstrated in the range 1 µgL−1 to 40 µgL−1. An improved lower limit of quantitation was achieved without use of complex sample extraction and clean-up procedures undertaken by other published methods. Excellent precision and accuracy results were achieved for dehydroabietic, chlorodehydroabietic, dichlorodehydroabietic, isopimaric (integrated inclusive of all C20H30O2 resin acids), dihydroisopimaric and 8(14)-abietenic resin acids, with t-99 percentile detection limits spanning the range 0.05 to 0.07 µgL−1. While measurement for the C20H30O2 resin acids by isopimaric equivalence is considered semi-quantitative and could be an under estimate for the abietic acid component, the developed method demonstrated clear advantage over time consuming, hazardous, and unstable derivatization procedures used for gas chromatography and capillary electrophoresis. The developed LC/QToF method was successfully transferred to an LC triple quadrupole mass spectrometer for routine high throughput trace level analysis. Real world samples, including sea water and estuary water, demonstrated excellent spike recoveries by this procedure, indicating that the method is well suited to the monitoring of industrially derived resin acids in environmental surface waters. While no interferences were observed during routine sample analysis using myristic-1-13C acid and palmitic-1-13C acid internal standards, these were later substituted by myristic-d27 and palmitic-d31 acid in order to improve method robustness for environmental samples where endogenous parent fatty acids could be present.

Terpene and resin acid contents in Scots pine stem lesions colonized by the rust fungus Cronartium pini

AbstractCronartium pini causes economic losses especially on Scots pine in northern Europe. Scots pine reacts to rust infection by resin flow. The chemicals enriched in wood after Cronartium infection have not been investigated before. We investigated resin acids and mono‐ and sesquiterpenes produced in Cronartium‐infected wood. Cronartium‐infected wood was extracted with acetone, and the extractives were analysed by GC‐mass spectrometry (GC‐MS) and compared to those from control wood. Among resin acids, abietic acid, levopimaric acid, palustric acid, dehydroabietic acid and neoabietic acid were the richest (32–68 mg/g) in Cronartium‐infected wood. Among monoterpenes, concentration of α‐pinene was the highest (49 mg/g) in Cronartium‐infected wood. Concentrations of all monoterpenes and resin acids and most sesquiterpenes were significantly higher (1.3‐ to 108‐fold) in Cronartium‐infected wood compared to control wood. In the control wood, the extractive content was greater (1.1‐ to 14‐fold) than in the literature suggesting that the chemical processes were strongly affected by the rust. The results suggest that terpenes and resin acids are produced by the host to protect it from Cronartium rust.

Extractive concentrations and cellular-level distributions change radially from outer to inner heartwood in Scots pine.

The heartwood of many wood species is rich in extractives, which improve the wood material's resistance to biological attack. Their concentration is generally higher in outer than inner heartwood, but the exact radial changes in aging heartwood remain poorly characterized. This investigation studied these radial changes in detail in Scots pine (Pinus sylvestris L.), using radial sample sequences prepared from three different trees. Stilbene and resin acid contents were first measured from bulk samples, after which the extractive contents of individual heartwood annual rings were investigated using Raman spectroscopy and fluorescence microscopy. Raman imaging and fluorescence microscopy were also used to study the cellular-level distributions of extractives in different annual rings. Although there were substantial differences between the trees, the content and distribution of stilbenes seemed to follow a general radial trend. The results suggest that stilbenes are absorbed into heartwood tracheid cell walls from small stilbene-rich extractive deposits over several years and then eventually transform into non-extractable compounds in aging heartwood. Resin acids followed no consistent radial trends, but their content was strongly connected to the frequency of large extractive deposits in latewood tracheid lumens. The results highlight the variability of heartwood extractives: their content and distribution vary not only between trees but also between and even within the annual rings of a single tree. This high variability is likely to have important effects on the properties of heartwood and the utilization of heartwood timber.

Hydrophobic and Hydrophilic Extractives in Norway Spruce and Kurile Larch and Their Role in Brown-Rot Degradation.

Extractives found in the heartwood of a moderately durable conifer (Larix gmelinii var. japonica) were compared with those found in a non-durable one (Picea abies). We identified and quantified heartwood extractives by extraction with solvents of different polarities and gas chromatography with mass spectral detection (GC-MS). Among the extracted compounds, there was a much higher amount of hydrophilic phenolics in larch (flavonoids) than in spruce (lignans). Both species had similar resin acid and fatty acid contents. The hydrophobic resin components are considered fungitoxic and the more hydrophilic components are known for their antioxidant activity. To ascertain the importance of the different classes of extractives, samples were partially extracted prior to subjection to the brown-rot fungus Rhodonia placenta for 2–8 weeks. Results indicated that the most important (but rather inefficient) defense in spruce came from the fungitoxic resin, while large amounts of flavonoids played a key role in larch defense. Possible moisture exclusion effects of larch extractives were quantified via the equilibrium moisture content of partially extracted samples, but were found to be too small to play any significant role in the defense against incipient brow-rot attack.

Resin acids as inducible chemical defences of pine seedlings against chewing insects.

Inducibility of defences in response to biotic stimuli is considered an important trait in plant resistance. In conifers, previous research has mostly focused on the inducibility of the volatile fraction of the oleoresin (mono- and sesquiterpenes), leaving the inducibility of the non-volatile resin acids largely unexplored, particularly in response to real herbivory. Here we investigated the differences in the inducibility of resin acids in two pine species, one native from Europe (Pinus pinaster Ait.) and another from North America (Pinus radiata D. Don), in response to wounding by two European insects: a bark chewer, the pine weevil (Hylobius abietis L.), and a defoliator, the pine processionary caterpillar (Thaumetopoea pityocampa Schiff.). We quantified the constitutive (control) and induced concentrations of resin acids in the stem and needles of both pine species by gas chromatography techniques. Both pine species strongly increased the concentration of resin acids in the stem after pine weevil feeding, although the response was greater in P. pinaster than in P. radiata. However, systemic defensive responses in the needles were negligible in both pine species after pine weevil feeding in the stem. On the other hand, P. radiata locally reduced the resin acid concentration in the needles after pine caterpillar feeding, whereas in P. pinaster resin acid concentration was apparently unaffected. Nevertheless, systemic induction of resin acids was only observed in the stem of P. pinaster in response to pine caterpillar feeding. In summary, pine induced responses were found highly compartmentalized, and specific to herbivore identity. Particularly, plant defence suppression mechanisms by the pine caterpillar, and ontogenetic factors might be potentially affecting the induced response of resin acids in both pine species.

Spatial variation in soil available water holding capacity alters carbon mobilization and allocation to chemical defenses along jack pine stems

Carbohydrate metabolism in trees has received considerable attention due to its role in global forest decline. However, mobilization, storage, and allocation of carbohydrates show large variation along tree stems due to various source-sink relationships. Currently, we have a limited understanding of the causes or consequences of carbohydrate variation on plant chemical defenses. We measured non-structural carbohydrates (NSC), monoterpenes, and diterpene resin acids along jack pine (Pinus banksiana) stems before inoculating with a phytopathogenic fungus in multiple sites with different soil available water holding capacities (AWHC). We then assessed induced defense responses in trees by measuring lesion areas (necrotic tissues), NSC mobilization, and terpene concentrations along different stem heights. Before inoculation, NSC concentrations increased with stem height, diterpene resin acid concentrations decreased, and monoterpene concentrations did not differ. However, with increasing AWHC, NSC concentrations decreased, monoterpene concentrations increased, and diterpene resin acid concentrations did not differ. After inoculation, trees on the high AWHC sites developed smaller lesions, mobilized local NSC, and induced higher monoterpene concentrations in the phloem and lesions. Diterpene resin acid concentrations did not differ with AWHC but differed at each stem height. Inoculation density showed no difference. We conclude that gradients in soil AWHC can affect stem vulnerability in jack pine trees by influencing carbon mobilization, allocation, and utilization.

High-Throughput 1H-Nuclear Magnetic Resonance-Based Screening for the Identification and Quantification of Heartwood Diterpenic Acids in Four Black Pine (Pinus nigra Arn.) Marginal Provenances in Greece.

A high-throughput quantitative Nuclear Magnetic Resonance 1H-NMR method was developed and applied to screen the quantity of the diterpenic resin acids in the heartwood of black pine, due to the renewed scientific interest in their medicinal properties and use in various diseases treatment. The 260 samples were taken from Pinus nigra clones, selected from four provenances of the Peloponnese (Greece), participating in a 35-year-old clonal seed orchard. Total resin acids per dry heartwood weight (dhw) varied greatly, ranging from 30.05 to 424.70 mg/gdhw (average 219.98 mg/gdhw). Abietic was the predominant acid (76.77 mg/gdhw), followed by palustric acid (47.94 mg/gdhw), neoabietic acid (39.34 mg/gdhw), and pimaric acid (22.54 mg/gdhw). Dehydroabietic acid was at moderate levels (11.69 mg/gdhw), while levopimaric, isopimaric, and sandaracopimaric acids were in lower concentrations. The resin acid fraction accounted for 72.33% of the total acetone extractives. Stilbenes were presented in significant quantities (19.70%). The resin acid content was composed mainly of the abietane type resin acids (83.56%). Peloponnesian Pinus nigra heartwood was found to be the richest source of resin acids identified to date and is considered the best natural source for the production of such bioactive extracts. The results indicate a high potential for effective selection and advanced breeding of pharmaceutical and high economic value bioactive substances from Pinus nigra clones.

Bark Assortments of Scots Pine and Norway Spruce as Industrial Feedstock for Tall Oil Production

Fatty and resin acids in bark residues generated by forest industries can be used to produce high-value green chemicals, but more information about their concentrations in potential sources is required. We examined variations in the content of lipophilic extractives from both pulpwood bark and timber bark of Norway spruce and Scots pine trees growing in homogenous stands in mid-Sweden. We found that spruce pulpwood bark had the highest total amounts of fatty and resin acids (average yield, 0.9 kg/m3 wood). The regression functions, based on readily available tree parameters (age, stem diameter, height, growth rate and inner bark proportions), can be used to predict the concentrations of fatty and resin acids, triglycerides, sterols and steryl esters in bark materials before harvesting stands that supply industrial plants.

Performance of resin bonded sand for magnesium alloy casting

The factors which affect performance of no-bake resin bonded sand (NBRBS) were investigated, including furan resin, curing agent and boric acid content and kinds of collapsibility agents and base sand. The results show that when the furan resin addition is 1.6wt% of base sand content and the curing agent addition is 50wt% of furan resin content, the comprehensive performance of NBRBS achieves optimization. The use of boric acid increases the curing speed, retained strength and gas evolution. The use of KI reduces the retained strength with a good tensile strength. When ceramacore being used as base sand, furan resin addition decreases greatly, and the tensile strength increases, gas evolution and retained strength both decrease, which can improve collapsibility of NBRBS. The SEM analysis demonstrates that the ceramacore particle is round, appeares standard sphere, and the ceramacore can form complete bonding film and bridge.

Hydrogen solubility measurements of analyzed tall oil fractions and a solubility model

Knowledge of hydrogen solubility in tall oil fractions is important for designing hydrotreatment processes of these complex nonedible biobased materials. Unfortunately measurements of hydrogen solubility into these fractions are missing in the literature.This work reports hydrogen solubility measured in four tall oil fractions between 373 and 597K and at pressures from 5 to 10MPa. Three of the fractions were distilled tall oil fractions their resin acids contents are respectively 2, 20 and 23 in mass-%. Additionally one fraction was a crude tall oil (CTO) sample containing sterols as the main neutral fraction. Measurements were performed using a continuous flow synthetic isothermal and isobaric method based on the visual observation of the bubble point. Composition of the flow was changed step-wise for the bubble point composition determination. We assume that the tall oil fractions did not react during measurements, based on the composition analysis performed before and after the measurements. Additionally the densities of the fractions were measured at atmospheric pressure from 293.15 to 323.15K.A Henry’s law model was developed for the distilled tall oil fractions describing the solubility with an absolute average deviation of 2.1%. Inputs of the solubility model are temperature, total pressure and the density of the oil at 323.15K. The solubility of hydrogen in the CTO sample can be described with the developed model with an absolute average deviation of 3.4%. The solubility of hydrogen increases both with increasing pressure and/or increasing temperature. The more dense fractions of the tall oil exhibit lower hydrogen solubility in comparison to the less dense fractions. The increase in the density of a fraction corresponds to an increased resin acid and sterol content of the sample. Sterols and resin acids exhibit lower hydrogen solubility in comparison to fatty acids.

Determination of rosin-size retention in wet-end process by quantifying the resin acid content in paper products

Determination of rosin-size retention in wet-end process by quantifying the resin acid content in paper products

Comparison of fatty and resin acid composition in boreal lodgepole pine and Scots pine for biorefinery applications

To investigate the potential for Scots- and lodgepole pine for biorefinery applications such as e.g., biodiesel and glue production, wood samples from five different sites in northern Sweden were compared. 21 fatty and 10 resin acids were detected by extraction and GC–MS analysis. Total fatty- and resin acid contents of Scots pine varied between 2.4 and 41.4mg/g. Corresponding concentrations for lodgepole pine were 2.3 and 26.0mg/g of dry material. Multivariate models were made with principal component analysis to take advantage of the multivariate correlations between the individual acids. Wood tissue type explained most of the variation in fatty and resin acid content, with heartwood having up to five times the extractive concentration of sapwood. Resin acids were mainly associated with heartwood, while fatty acids were more associated with sapwood. A five-component PLSDA-model distinguished between the two species, mainly due to differences in their hexadecanoic and heptadecanoic acid contents. Heartwood from Scots pine is more suitable for resin extraction while lodgepole pine is a better option for fatty- and resin acid extraction because of the extractives’ evenly distribution between wood types. Around 150kg of fatty acids and 1 ton of resins can be harvested per hectare from a typical mature boreal lodgepole pine stand, for biorefinery use. Systematic fractionation and selection of heartwood and sapwood will likely optimize industrial applications (e.g. biodiesel production) of each fraction.

Study of stilbene and resin acid content of Scots pine heartwood by electrical impedance spectroscopy (EIS)

Abstract Scots pine (Pinus sylvestris L.) heartwood samples were measured with electrical impedance spectroscopy (EIS) at frequency range 1 Hz–10 MHz in green and relative humidity (RH) 65% conditioned moisture content (MC) after oven-drying. Complex impedance parameters were studied in relation to the density, moisture, resin acid and stilbene contents. The measurements were conducted in tangential (T) and longitudinal (L) directions with 36 samples in each analysis. For green MC, there were significant correlations between impedance phase angle and contents of stilbenes and resin acids at frequencies below 400 Hz. For the resin acid content, the strongest correlation with phase-angleT was -0.45 (P<0.01) at 100 Hz. Impedance magnitude correlated significantly with MC throughout the frequency range, e.g., at 10 kHz, r was -0.71 (P<0.001) for L-direction. In moisture conditioned state, the correlation between stilbenes and T-measured phase angle was strongest at 250 Hz, (r=-0.56, P<0.001). Equivalent circuit model of two ZARC-Cole elements in series was fitted for the measurements in green MC. Several model parameters correlated with MC (e.g., R1, L r=-0.64, P<0.001), but only one parameter correlated weakly with stilbene content (R2, T r=0.35, P<0.05). The study shows that EIS has a potential for independent determination of resin acid or stilbene contents and MC for green pine heartwood.

Organic/elemental carbon and woodsmoke tracer concentrations following a community wide woodstove changeout program

Abstract As part of the Libby, Montana community-wide woodstove changeout program conducted between 2005 and 2008, nearly 1200 older model woodstoves were replaced with cleaner burning devices such as EPA-certified stoves. The reduction in overall ambient wintertime PM 2.5 mass has been documented. However, much less is known about the changes in the chemical (specifically the organic) makeup of the ambient particles as the emission sources changed within the community with the implementation of the cleaner-burning home heating devices. Overall, PM 2.5 mass levels decreased by 25%, while Total Carbon (TC) showed a 26% reduction when comparing the pre- and post-changeout concentrations. As the TC fraction is heavily influenced by Organic Carbon (OC) in Libby, trends were similar. Differential effects were observed for OC fractions according to analytical temperatures. Concentrations of Elemental Carbon (EC) were fairly consistent throughout the changeout, and did not show a dramatic reduction similar to the measured OC. Results from the polar organic compound program showed that the majority of the secondary aerosols were reduced, as were the majority of the woodsmoke markers such as levoglucosan and several methoxyphenols. However, the concentrations of resin acids actually increased following the woodstove changeout, suggesting that the chemistry of the particles have been altered as a result of this community-wide intervention.

Disengtangling the evolution of weak warning signals: high detection risk and low production costs of chemical defences in gregarious pine sawfly larvae

Evolution of costly secondary defences for a cryptic prey is puzzling, if the prey is already well protected by camouflage. However, if the chemical defence is not sufficient to deter all predators, selection can favour low signal intensity in defended prey. Alternatively, if the costs of chemical defence are low or cost-free, chemical defences can be expected to evolve also for non-signalling prey, particularly if conspicuous signalling is costly. We tested these assumptions with pine sawfly larvae (Neodiprion sertifer and Diprion pini) that are cryptically coloured and chemically defended with resin acids sequestered from their host plant (Pinus sp.). Larvae feed in large aggregations, which we hypothesise could function as a signal of unprofitability. Our results show that even though the birds found N. sertifer larvae unprofitable in the controlled laboratory assays, they continued attacking and consuming them in the wild. When we tested the signal value of aggregation we found that a large group size did not offer protection for a defended larva: the survival was higher in groups of 10 individuals compared to groups of 50, suggesting increased detectability costs for individuals in larger groups. Finally, we tested how costly the production and maintenance of a chemical defence is for D. pini larvae by manipulating the resin acid content of the diet. We did not find any life history or immunological costs of the chemical defence for the larvae. In contrast, pupal weights were higher on the high resin diet than on the low resin diet. Also, larvae were able to produce higher amounts of defence fluids on the high diet than on the low diet. Thus, our result suggests high detectability costs and low production costs of defences could explain why some unprofitable species have not evolved conspicuous signals.

Prediction of Resin and Fatty Acid Content of Biorefinery Feedstock by On-line Near-Infrared (NIR) Spectroscopy

Extractives in biorefinery feedstock are a source of precursor chemicals and biofuel products. Resin and fatty acids (RFAs) in such extractives constitute an interesting fraction, which may contain...

Dissolution and spatial distribution of resin acids and retene in sediments contaminated by pulp and paper industry

Wood extractives in sediments originating from the wood industry may interfere with benthic biota in aquatic environments. The research area was the Aanekoski watercourse in Central Finland, which has been affected by the chemical wood industry for over a century. The goal was to determine the dissolution potency of resin acids (RAs) and their derivative, retene, in the sediment, and their current vertical and spatial stratification to assess the load due to potential erosion. Sediments were collected from two upstream reference sites and three lake-like basins, located as far as 33 km downstream from the mills. The dissolution potency was studied by two different agitation times and temperatures from sediment-water (1+4 v/v) elutriates. The vertical distribution of extractives was determined from the uppermost 20 cm of sediment. Using spatial interpolation, the distribution of extractives was estimated from two upper sediment layers (0–2 and 2–5 cm) downstream from the source. According to the interpolation, the total amount of dehydroabietic (DHAA) and isopimaric acids (IPA) were calculated as kg/ha in the whole sediment area. The total concentration of RAs in the surface sediment reached up to 168 µg/g dw, and they were found to desorb to water up to 77 µg/l. The concentrations of retene were low both in the sediment (<51 µg/g dw) and elutriate (<0.53 µg/l). Spatial interpolation showed that the highest calculated amounts of the most abundant RAs were in Kuhnamo basin, in the sediment layer 2–5 cm; the estimated amount of DHAA and IPA were approximately 440 and 85 kg/ha, respectively. Disturbances may change the exposure situation, causing desorption of sediment-associated compounds in levels that may be harmful to aquatic animals. The amount of desorption varies depending on the concentration of contaminants in sediment, the nature of disturbance, and the sediment organic carbon content. Low retene concentrations can be explained by oxic conditions and low abundance of RAs in the sediments.