Anthraquinones from the Fungus Dermocybe sanguinea as Textile Dyes

This study is based on the multidiciplinary approach of using natural colorants as textile dyes. The author was interested in both the historical and traditional aspects of natural dyeing as well as the modern industrial applications of the pure natural compounds. In the study, the anthraquinone compounds were isolated as aglycones from the ectomycorrhizal fungus Dermocybe sanguinea. The endogenous beta-glucosidase of the fungus was used to catalyse the hydrolysis of the O-glycosyl linkage in emodin- and dermocybin-1-beta-D-glucopyranosides. The method, in which 10.45 kg of fresh fungi was starting material, yielded two fractions: 56.0 g of Fraction 1 (94% of the total amount of pigment,) consisting almost exclusively of the main pigments emodin and dermocybin, and 3.3 g of Fraction 2 (6%) consisting mainly of the anthraquinone carboxylic acids. The anthraquinone compounds in Fractions 1 and 2 were separated by one- and two-dimensional thin-layer-chromatography (TLC) using silica plates. 1D TLC showed that neither an acidic nor a basic solvent system alone separated completely all the anthraquinones isolated from D. sanguinea, in spite of the variation of the rations of the solvent components in the systems. Thus, a new 2D TLC technique was developed, applying n-pentanol-pyridine-methanol (6:4:3, v/v/v) and toluene-ethyl acetate-ethanol-formic acid (10:8:1:2, v/v/v/v) as eluents. Fifteen different anthraquinone derivatives were completely separated from one another. Emodin, physcion, endocrocin, dermolutein, dermorubin, 5-chlorodermorubin, emodin-1-beta-D-glucopyranoside, dermocybin-1-beta-D-glucopyranoside and dermocybin, and five new compounds, not earlier identified in D. sanguinea, 7-chloroemodin, 5,7-dichloroemodin, 5,7-dichloroendocrocin, 4-hydroxyaustrocorticone and austrocorticone, were separated and identified on the basis of their Rf-values, UV/Vis spectra and mass spectra. One substance remained unidentified, because of its very low concentration. The anthraquinones in Fractions 1 and 2 were preparatively separeted by liquid-liquid partition, with isopropylmethyl ketone and aqueous phosphate buffer as the solvent system. Advantage was taken of the principle of stepwise pH-gradient elution. The multiple liquid-liquid partition (MLLP) offered an excellent method for the preparative separation of compounds, which contain acidic groups such as the phenolic OH and COOH groups. Due to their strong aggregation properties, these compounds are, without derivatization, very difficult to separate on a preparative scale by chromatographic methods. By the MLLP method remarkable separations were achieved for the components in each mixture. Emodin and dermocybin were both obtained from Fraction 1 in a purity of at least 99%. Pure emodin and dermocybin were applied as mordant dyes to wool and polyamide and as disperse dyes to polyester and polyamide, using the high temperature (HT) technique. A mixture of dermorubin and 5-chlorodermorubin was applied as an acid dye to wool. In these experiments, synthetic dyes were used as references. Experiments were also performed using water extract of the air-dried fungi as dye liquor for wool and silk. The main colouring compounds in the crude water extract were emodin and dermocybin, which indicated that the O-glycosyl linkages in emodin- and dermocybin-1-beta-D-glucopyranosides were broken by the beta-glucosidase enzyme. Apparently, the hydrolysis occurred during the drying of the fungi and during the soaking of the dried fruit bodies overnight when preparing the dyebath. The colour of each dyed material was investigated in terms of the CIELAB L*, a* and b* values, and the colour fastness to light, washing and rubbing was tested according to the ISO standards. In the mordant dyeing experiments, emodin dyed wool and polyamide yellow and red, depending on the pH of the dyebath. Dermocybin gave purple and violet colours. The colour fastness of the mordant-dyed fabrics varied from good to moderate. The fastness properties of the natural anthraquinone carboxylic acids on wool were good, indicating the strength of the ionic bonds between the COO- groups of the dyes and the NH3+ groups of the fibres. In the disperse dyeing experiments, emodin dyed polyester bright yellow and dermocybin bright reddish-orange, and the fabrics showed excellent colour fastness. In contrast, emodin and dermocybin successfully dyed polyamide brownish-orange and wine-red, respectively, but with only moderate fastness. In industrial dyeing processes, natural anthraquinone aglycone mixtures dyed wool and silk well even at low concentrations of mordants, i.e. with 10% of the weight of the fibre (owf) of KAl(SO4)2 and 1 or 0.5% owf of other mordants. This study showed that purified natural anthraquinone compounds can produce bright hues with good colour-fastness properties in different textile materials. Natural anthraquinones have a significant potential for new dyeing techniques and will provide useful alternatives to synthetic dyes.

Road Dust from Pavement Wear and Traction Sanding

Vehicles affect the concentrations of ambient airborne particles through exhaust emissions, but particles are also formed in the mechanical processes in the tire-road interface, brakes, and engine. Particles deposited on or in the vicinity of the road may be re-entrained, or resuspended, into air through vehicle-induced turbulence and shearing stress of the tires. A commonly used term for these particles is road dust . The processes affecting road dust emissions are complex and currently not well known. Road dust has been acknowledged as a dominant source of PM10 especially during spring in the sub-arctic urban areas, e.g. in Scandinavia, Finland, North America and Japan. The high proportion of road dust in sub-arctic regions of the world has been linked to the snowy winter conditions that make it necessary to use traction control methods. Traction control methods include dispersion of traction sand, melting of ice with brine solutions, and equipping the tires with either metal studs (studded winter tires), snow chains, or special tire design (friction tires). Several of these methods enhance the formation of mineral particles from pavement wear and/or from traction sand that accumulate in the road environment during winter. When snow and ice melt and surfaces dry out, traffic-induced turbulence makes some of the particles airborne. A general aim of this study was to study processes and factors underlying and affecting the formation and emissions of road dust from paved road surfaces. Special emphasis was placed on studying particle formation and sources during tire road interaction, especially when different applications of traction control, namely traction sanding and/or winter tires were in use. Respirable particles with aerodynamic diameter below 10 micrometers (PM10) have been the main concern, but other size ranges and particle size distributions were also studied. The following specific research questions were addressed: i) How do traction sanding and physical properties of the traction sand aggregate affect formation of road dust? ii) How do studded tires affect the formation of road dust when compared with friction tires? iii) What are the composition and sources of airborne road dust in a road simulator and during a springtime road dust episode in Finland? iv) What is the size distribution of abrasion particles from tire-road interaction? The studies were conducted both in a road simulator and in field conditions. The test results from the road simulator showed that traction sanding increased road dust emissions, and that the effect became more dominant with increasing sand load. A high percentage of fine-grained anti-skid aggregate of overall grading increased the PM10 concentrations. Anti-skid aggregate with poor resistance to fragmentation resulted in higher PM levels compared with the other aggregates, and the effect became more significant with higher aggregate loads. Glaciofluvial aggregates tended to cause higher particle concentrations than crushed rocks with good fragmentation resistance. Comparison of tire types showed that studded tires result in higher formation of PM emissions compared with friction tires. The same trend between the tires was present in the tests with and without anti-skid aggregate. This finding applies to test conditions of the road simulator with negligible resuspension. Source and composition analysis showed that the particles in the road simulator were mainly minerals and originated from both traction sand and pavement aggregates. A clear contribution of particles from anti-skid aggregate to ambient PM and dust deposition was also observed in urban conditions. The road simulator results showed that the interaction between tires, anti-skid aggregate and road surface is important in dust production and the relative contributions of these sources depend on their properties. Traction sand grains are fragmented into smaller particles under the tires, but they also wear the pavement aggregate. Therefore particles from both aggregates are observed. The mass size distribution of traction sand and pavement wear particles was mainly coarse, but fine and submicron particles were also present.