Evaluation of Physico-Chemical Characteristics of Cement Superplasticizer Based on Polymelamine Sulphonate.

Cementitious materials are used to construct an engineered barrier in repositories for radioactive waste. The cement matrix may contain a variety of organic compounds, some of which are polymeric admixtures used as plasticizers. Superplasticizers (SPs) are highly effective organic cement additives for reducing water amount, increasing workability, homogeneity, plasticity and the non-segregation of mortars and grouts, improving mechanical properties and resistance to destructive environments. SPs in cement could have an impact on the long-term safety of the disposals of radioactive waste. These organic agents can leach from the cementitious matrix into groundwater and may affect the migration behaviour of radionuclides. The detailed chemical composition and other characteristics of the cement (CEM I 42.5 R, Sweden) used for the leaching experiments were evaluated. It contained mainly CaO (52.51 ± 1.37, %), and the surface area of the cement particles was 13.2 ± 1.3 m2/g. An insignificant increase in pH (from 12.6 ± 0.1 to 12.8 ± 0.1) was observed for the leachates over 10 days. A commercially available cement superplasticizer based on polymelamine sulphonate (PMS) Peramin SMF10 (Peramin AB, Sweden) was chosen for the research. The product's chemical composition was analysed using wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, while other physico-chemical properties of the PMS superplasticizer were assessed by Raman spectroscopy and thermo-gravimetric analysis. In aqueous solutions and powders of PMS, the same most intensive features were observed at 774 cm-1 (ring out-of-plane deformation), 977 cm-1 (C-N-C bending, SO stretching) and 1055 cm-1 (C-N=C bending) in the Raman spectra. At up to 270 °C, the polymer was thermally stable. Raman and UV/Vis spectroscopies were used to assess the rate of the alkaline degradation of PMS superplasticizer in different aqueous solutions. No changes were observed in the hydrolytic solutions with any of the above analytical methods over a period of 3 years. The results obtained revealed a good thermal and chemical stability (in highly alkaline media, pH = 9.9-12.9) of the PMS polymer.

Phytochemical Composition and Antioxidant Activity of Various Extracts of Fibre Hemp (Cannabis sativa L.) Cultivated in Lithuania.

The phytochemistry of fibre hemp (Cannabis sativa L., cv. Futura 75 and Felina 32) cultivated in Lithuania was investigated. The soil characteristics (conductivity, pH and major elements) of the cultivation field were determined. The chemical composition of hemp extracts and essential oils (EOs) from different plant parts was determined by the HPLC/DAD/TOF and GC/MS techniques. Among the major constituents, ß-caryophyllene (≤46.64%) and its oxide (≤14.53%), α-pinene (≤20.25%) or α-humulene (≤11.48) were determined in EOs. Cannabidiol (CBD) was a predominant compound (≤64.56%) among the volatile constituents of the methanolic extracts of hemp leaves and inflorescences. Appreciable quantities of 2-monolinolein (11.31%), methyl eicosatetraenoate (9.70%) and γ-sitosterol (8.99%) were detected in hemp seed extracts. The octadecenyl ester of hexadecenoic acid (≤31.27%), friedelan-3-one (≤21.49%), dihydrobenzofuran (≤17.07%) and γ-sitosterol (14.03%) were major constituents of the methanolic extracts of hemp roots, collected during various growth stages. The CBD quantity was the highest in hemp flower extracts in pentane (32.73%). The amounts of cannabidiolic acid (CBDA) were up to 24.21% in hemp leaf extracts. The total content of tetrahydrocannabinol (THC) isomers was the highest in hemp flower pentane extracts (≤22.43%). The total phenolic content (TPC) varied from 187.9 to 924.7 (average means, mg/L of gallic acid equivalent (GAE)) in aqueous unshelled hemp seed and flower extracts, respectively. The TPC was determined to be up to 321.0 (mg/L GAE) in root extracts. The antioxidant activity (AA) of hemp extracts and Eos was tested by the spectrophotometric DPPH● scavenging activity method. The highest AA was recorded for hemp leaf EOs (from 15.034 to 35.036 mmol/L, TROLOX equivalent). In the case of roots, the highest AA (1.556 mmol/L, TROLOX) was found in the extracts of roots collected at the seed maturation stage. The electrochemical (cyclic and square wave voltammetry) assays correlated with the TPC. The hydrogen-peroxide-scavenging activity of extracts was independent of the TPC.

Palladium-Catalyzed Synthesis of Cyclopropylthiophenes and Their Derivatization.

The cyclopropylthiophene moiety has attracted the attention of the scientific community for its potential pharmaceutical applications. However, synthesis of the compounds containing this framework remains challenging, has rarely been reported and remains unresolved. Here we provide optimized syntheses for cyclopropylthiophenes and their derivatives, containing carbonyl, acetyl, carboxylic acid, methyl carboxylate, nitrile, bromide and sulfonyl chloride moieties.

Allelopathic Activity of Canadian Goldenrod (Solidago canadensis L.) Extracts on Seed Germination and Growth of Lettuce (Lactuca sativa L.) and Garden Pepper Cress (Lepidium sativum L.).

Native to N. America, Canadian goldenrod (Solidago canadensis L.) was introduced to Europe as an ornamental plant and quickly spread here and in other parts of the world. The rapid spread of the plant is due to several reasons: phenotypic plasticity, broad climatic tolerance, propagation via underground rhizomes and seeds that mature in large numbers, etc. Additionally, the success of Canadian goldenrod's invasion is determined by its allelochemicals that affect seed germination, root formation and whole growth of nearby plants. Allelopathy of various extracts and essential oils (EOs) of S. canadensis on seed germination and growth of lettuce (Lactuca sativa L.) and garden pepper cress (Lepidium sativum L.) was evaluated and compared with other Solidago species (S. virgaurea, S. × niederederi) collected from the same growing locality in Lithuania. Soil characteristics (conductivity, pH and major elements) of the collecting site were determined. Aqueous flower extracts of all studied Solidago species showed the highest inhibitory effect on model plants. Canadian goldenrod leaf water/diethyl ether extract showed highest inhibitory effect in all relative concentrations (1.0; 0.1; 0.01) suppressing growth of L. sativa (from 0 to 2.3 mm compared with 22.7 mm for control samples) and L. sativum (from 0.5 to 16.8 mm compared with 35.3 mm in control). It was noticed that garden pepper cress was more susceptible to Solidago spp. inhibitory effects than lettuce. S. canadensis root EOs comprised mainly of limonene (35.0%) and ß-pinene (26.2%) and inflorescence oils containing α-pinene (21.6%), germacrene D (15.1%), limonene (10.2%) and lupenyl acetate (9.8%) exhibited the highest inhibitory effect on lettuce and garden pepper cress growth. Relative germination and vigor index of model plants was conducted. Chemical composition of extracts and EOs was determined by HPLC/DAD/TOF and GC/MS techniques.

Ionomic Parameters of Populations of Common Juniper (Juniperus communis L.) Depending on the Habitat Type.

For the study of the ionomic parameters of Juniperus communis needles, fourteen sites covering most of the territory of Lithuania and belonging to distinct habitats (coastal brown dunes covered with natural Scots pine forests (G), Juniperus communis scrubs (F), transition mires and quaking bogs (D), subcontinental moss Scots pine forests (G), and xero-thermophile fringes) were selected. Concentrations of macro-, micro-, and non-essential elements were analyzed in current-year needles, sampled in September. According to the concentrations of elements in J. communis needles, the differences between the most contrasting populations were as follows: up to 2-fold for Mg, N, K, Ca, and Zn; 2- to 7-fold for P, Na, Fe, Cu, Al, Cr, Ni, and Pb; and 26- to 31-fold for Mn and Cd. The concentrations of Cd, Cr, and Ni in needles of J. communis did not reach levels harmful for conifers. When compared to all other habitats (B, F, G, and E), the populations from transition mires and quaking bogs (D) had significantly lower concentrations of main nutritional elements N (12176 µg/g d. m.), P (1054 µg/g d. m.), and K (2916 µg/g d. m.). In Juniperus communis scrubs (F), a habitat protected by EUNIS, the concentration of K in the needles was highest, while Zn and Cu concentrations were the lowest. Principal component (PC) analyses using concentrations of 15 elements as variables for the discrimination of populations or habitats allowed authors to distinguish F and B habitats from the E habitat (PC1) and F and D habitats from the G habitat (PC2). Discriminating between populations, the most important variables were concentrations of P, N, Mg, Ca, Cu, and K. Discriminating between habitats, the important variables were concentrations of N and P.

Patterns of Phenolic Compounds in Betula and Pinus Pollen.

In this study, phenolic compounds and their antioxidant activity in the pollen of anemophilous Betula and Pinus were determined. Spectrophotometric, high-performance thin-layer and liquid chromatography methods were applied. Free phenolic compounds (free PC) and phenolic compounds bound to the cell wall (bound PC) were analysed in the pollen extracts. Regardless of the pollen species, their content was 20% higher than that in bound PC extracts. Pinus pollen extracts contained 2.5 times less phenolic compounds compared to Betula. Free PC extraction from the deeper layers of Pinus pollen was minimal; the same content of phenolic compounds was obtained in both types of extracts. The bioactivity of pollen (p < 0.05) is related to the content of phenolic compounds and flavonoids in Betula free PC and in bound PC, and only in free PC extracts of Pinus. Rutin, chlorogenic and trans-ferulic acids were characterised by antioxidant activity. Phenolic acids accounted for 70−94%, while rutin constituted 2−3% of the total amount in the extracts. One of the dominant phenolic acids was trans-ferulic acid in all the Betula and Pinus samples. The specific compounds were vanillic and chlorogenic acids of Betula pollen extracts, while Pinus extracts contained gallic acid. The data obtained for the phenolic profiles and antioxidant activity of Betula and Pinus pollen can be useful for modelling food chains in ecosystems.

Enrichment of Water Bodies with Phenolic Compounds Released from Betula and Pinus Pollen in Surface Water.

Betula and Pinus pollen, which are dispersed in natural surface waters, release biologically active compounds into the water bodies. This study aims to evaluate variations in the distribution and composition of phenolic compounds in suspended particles in natural water bodies during pollen spreading. Samples taken from water bodies of different trophic levels were analyzed by microscopy, UV/VIS spectroscopy, HPTLC, and HPLC/DAD. The study revealed that the total phenolic content in water-suspended particles varied from 3.0 mg/g to 11.0 mg/g during Betula and Pinus pollen spreading. It was also observed that the surface water of dystrophic natural lakes had a higher content of phenolic compounds than the eutrophic, hypereutrophic, and mesotrophic water bodies. Chlorogenic, trans-ferulic, vanillin, and 3,4-dihydroxybenzoic acids were frequently detected in the surface water samples. Experimental measurements have shown variations in the release of phenolic compounds from Betula pollen into water (p < 0.05). After the exhibition of pollen, the distilled water predominantly contained bioactive chlorogenic acid. Further in situ investigations are necessary to gain a more comprehensive understanding of the function of phenolic compounds in aquatic ecosystems. The exploration of the release of bioactive compounds from pollen could provide valuable insights into the potential nutritional value of pollen as a nutrient source for aquaculture.

In Vitro Antioxidant and Prooxidant Activities of Red Raspberry (Rubus idaeus L.) Stem Extracts.

Leaves and stems of red raspberry (Rubus idaeus) are used in Lithuanian folk medicine. Healing properties of raspberry are related to the content of bioactive compounds, mainly polyphenols. Extracts of raspberry leaves contained higher total phenolic content (TPC) (1290 mg/L, expressed in gallic acid equivalent) compared to that in extracts of stems or peeled bark (up to 420 mg/L and 598 mg/L, respectively). To find out whether the collection time of herbal material was critical for the properties of the extracts, the stems were collected at different times of the year. TPC in the extracts depended more on extraction conditions rather than on the sampling time. Antioxidant activity of raspberry stem and bark extracts tested by spectrophotometric (DPPH● scavenging) and electrochemical (cyclic and differential pulse voltammetry) assays correlated with TPC. DPPH radical scavenging activity values for stem, leaf, and bark extracts were as follows: ≤1.18 ± 0.07, 1.63 ± 0.10, and ≤1.90 ± 0.04 (mmol/L, TROLOX equivalent), respectively. Assessed electrochemically, hydrogen peroxide-scavenging activity of extracts was independent on TPC. The latter activity was related to the presence of some protein in the extract as revealed by gel electrophoresis. Prooxidant activity of raspberry stem extracts was dependent on solution pH and temperature.

Antioxidant and Toxic Activity of Helichrysum arenarium (L.) Moench and Helichrysum italicum (Roth) G. Don Essential Oils and Extracts.

Helichrysum arenarium (L.) Moench (sandy everlasting) is the only species from genus Helichrysum Mill that grows spontaneously in Lithuania. The chemical composition of the essential oils (EOs) from inflorescences and leaves of H. arenarium wild plants was analysed by GC-MS. Palmitic (≤23.8%), myristic (≤14.9%) and lauric (6.1%) acids, n-nonanal (10.4%), and trans-ß-caryophyllene (≤6.5%) were the major constituents in the EOs. For comparison, the main components in EO from flowers (commercial herb material) of H.italicum were γ-curcumene (21.5%), ß-selinene (13.6%), α-selinene (8.1%), ß-eudesmol (8.3%), and α-pinene (6.5%). Composition of H. arenarium methanolic extracts was investigated by HPLC-DAD-TOF. The main compounds were the following: luteolin-7-O-glucoside, naringenin and its glucoside, apigenin, chlorogenic acid, arenol, and arzanol. Antioxidant activity of EOs and extracts was tested by DPPH● and ABTS●+ assays. Sandy everlasting extracts exhibited significantly higher radical scavenging activities (for leaves 11.18 to 19.13 and for inflorescences 1.96 to 6.13 mmol/L TROLOX equivalent) compared to those of all tested EOs (0.25 to 0.46 mmol/L TROLOX equivalent). Antioxidant activity, assayed electrochemically by cyclic and square wave voltammetry correlated with total polyphenolic content in extracts and radical scavenging properties of EOs and extracts. The toxic activity of EOs of both Helichrysum species was evaluated using a brine shrimp (Artemia salina) bioassay. H. italicum inflorescence EO was found to be toxic (LC50 = 15.99 µg/mL) as well as that of H. arenarium (LC50 ≤ 23.42 µg/mL) oils.

Toxic, Radical Scavenging, and Antifungal Activity of Rhododendron tomentosum H. Essential Oils.

The chemical composition of eight (seven shoot and one inflorescence) essential oils (EOs) of Rh. tomentosum H. plants growing in Eastern Lithuania is reported. The plant material was collected during different phases of vegetation (from April to October). The oils were obtained by hydrodistillation from air-dried aerial parts (leaves and inflorescences). In total, up to 70 compounds were identified by GC-MS and GC (flame-ionization detector, FID); they comprised 91.0 ± 4.7%-96.2 ± 3.1% of the oil content. Sesquiterpene hydrocarbons (54.1 ± 1.5%-76.1 ± 4.5%) were found to be the main fraction. The major compounds were palustrol (24.6 ± 2.6%-33.5 ± 4.4%) and ledol (18.0 ± 2.9%-29.0 ± 5.0%). Ascaridol isomers (7.0 ± 2.4%-14.0 ± 2.4% in three oils), myrcene (7.2 ± 0.3% and 10.1 ± 1.3%), lepalol (3.3 ± 0.3% and 7.9 ± 3.0%), and cyclocolorenone isomers (4.1 ± 2.5%) were determined as the third main constituents. The toxic activity of marsh rosemary inflorescence and shoot oils samples was evaluated using a brine shrimp (Artemia sp.) bioassay. LC50 average values (11.23-20.50 µg/mL) obtained after 24 h of exposure revealed that the oils were notably toxic. The oil obtained from shoots gathered in September during the seed-ripening stage and containing appreciable amounts of palustrol (26.0 ± 2.5%), ledol (21.5 ± 4.0%), and ascaridol (7.0 ± 2.4%) showed the highest toxic activity. Radical scavenging activity of Rh. tomentosum EOs depended on the plant vegetation stage. The highest activities were obtained for EOs isolated from young shoots collected in June (48.19 ± 0.1 and 19.89 ± 0.3 mmol/L TROLOX (6-hydroxy-2,5,7,8-tetra-methylchromane-2-carboxylic acid) equivalent obtained by, respectively, ABTS•+ (2,2'-amino-bis(ethylbenzothiazoline-6-sulfonic acid) diammonium salt) and DPPH•(2,2-diphenyl-1-picrylhydrazyl) assays). Agar disc diffusion assay against pathogenic yeast Candida parapsilosis revealed the potential antifungal activity of EOs. An alternative investigation of antifungal activity employed mediated amperometry at yeast Saccharomyces cerevisiae-modified electrodes. The subjection of yeast cells to vapors of EO resulted in a three to four-fold increase of electrode responses due to the disruption of yeast cell membranes.

Chemical Polymorphism of Essential Oils of Artemisia vulgaris Growing Wild in Lithuania.

Compositional variability of mugwort (Artemisia vulgaris L.) essential oils has been investigated in the study. Plant material (over ground parts at full flowering stage) was collected from forty-four wild populations in Lithuania. The oils from aerial parts were obtained by hydrodistillation and analyzed by GC(FID) and GC/MS. In total, up to 111 components were determined in the oils. As the major constituents were found: sabinene, 1,8-cineole, artemisia ketone, both thujone isomers, camphor, cis-chrysanthenyl acetate, davanone and davanone B. The compositional data were subjected to statistical analysis. The application of PCA (Principal Component Analysis) and AHC (Agglomerative Hierarchical Clustering) allowed grouping the oils into six clusters. AHC permitted to distinguish an artemisia ketone chemotype, which, to the best of our knowledge, is very scarce. Additionally, two rare cis-chrysanthenyl acetate and sabinene oil types were determined for the plants growing in Lithuania. Besides, davanone was found for the first time as a principal component in mugwort oils. The performed study revealed significant chemical polymorphism of essential oils in mugwort plants native to Lithuania; it has expanded our chemotaxonomic knowledge both of A. vulgaris species and Artemisia genus.

Compositional Variability and Toxic Activity of Mugwort (Artemisia vulgaris) Essential Oils.

The compositional variability of the essential oils of aerial parts of mugwort (Artemisia vulgaris L.), collected from fifteen wild populations in Lithuania is detailed. The most predominant components were davanones (13.8-45.5%, six oils), germacrene D (9.1-30.5%, four oils), 1,8-cineole (16.4%, one oil), camphor (18.9%, one oil), trans-thujone (8.9 and 10.9%, two oils) and cis-chrysanthenyl acetate (10.4%, one oil). To the best of our knowledge, the davanone chemotype for A. vulgaris oils is described for the first time. The toxicity of the mugwort essential oils was determined using brine shrimp (Anemia sp.) assay. LC0 values (10.3-23.1 µg/mL) obtained for the oils after 24 h of exposure revealed that the oils containing appreciable amounts of germacrene D, 1,8-cineole, camphor and davanone were notably toxic.

Variability, toxicity, and antioxidant activity of Eupatorium cannabinum (hemp agrimony) essential oils.

CONTENT: Eupatorium cannabinum L. (Asteraceae) is as a potential source of biologically active compounds. The plant is used in traditional medicine for the treatment of diarrhea and livers diseases. OBJECTIVE: The present study provides investigation on pharmacological properties (antioxidant and toxic activities) of essential oils of E. cannabinum, collected from 11 wild populations in Lithuania. MATERIALS AND METHODS: Twenty-two hemp agrimony essential oil samples were prepared by hydrodistillation according to the European Pharmacopoeia, and their chemical composition was determined by GC-FID and GC-MS. Compositional data were subjected to principal components analysis (PCA). Instead of conventional spectrophotometric methods, cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques were applied to determine antioxidant activity of hemp agrimony essential oils. Meanwhile, toxicity of the oils was determined using brine shrimp (Artemia sp.) assay. RESULTS: Chemical profiles of E. cannabinum oils were described according to the first predominant components: germacrene D (≤22.0%), neryl acetate (≤20.0%), spathulenol (≤27.2%), and α-terpinene (11.5%). For the first time, α-zingiberene (≤7.8%) was found to be among three major constituents (as the second one) for hemp agrimony oils. SWV measurements revealed that oxidation potentials of compounds present in the oils are lower (below 0.1 V) compared with that of well-known antioxidant quercetin (0.15 V). Toxicity tests evaluated that hemp agrimony oils containing predominant amounts of germacrene D and neryl acetate were notably toxic (LC50 value 16.3-22.0 µg/mL). CONCLUSION: The study provided some new data concerning chemical composition and pharmaceutical properties of E. cannabinum essential oils.

Composition of seed essential oils of Rhododendron tomentosum.

For the first time, the chemical composition of the seed essential oil of Rhododendron tomentosum was determined. Forty-seven compounds were identified, comprising 91.7% of the total oil. Palustrol (38.3%) and ledol (27.0%) were the predominant constituents. Some constituents, such as beta-pinene oxide, iso-menthyl acetate, nerolidyl acetate, cadalene and guaiazulene were characteristic only for the seeds and were identified for the first time in Rh. tomentosum oils. For comparison purposes, the essential oil isolated from the shoots of the same plant were analyzed [GC(FID) in combination with RIs, GC-MS and 13C NMR]. More than a half of the oil was comprised of ledol (36.5%) and palustrol (21.0%). Quantitative analysis of ascaridol, a heat-sensitive compound, was carried out by 13C NMR spectroscopy. Indeed, ascaridol undergoes partial thermal isomerization to iso-ascaridol during GC analyses.

Caryophyllene oxide-rich essential oils of Lithuanian Artemisia campestris ssp. campestris and their toxicity.

The chemical composition of the essential oils of aerial parts of Artemisia campestris ssp. campestris, collected from ten different locations in Lithuania is detailed in this paper. The major component in all the oils was caryophyllene oxide (8.5-38.8%), whereas compounds with the caryophyllane skeleton ranged from 10.2 to 44.5%. Other representative constituents were germacrene D (< or = 15.0%), humulene epoxide II (< or = 8.1%), beta-ylangene (< or = 7.7%), spathulenol (< or = 6.8%), beta-elemene (< or = 6.8%), beta-caryophyllene (< or = 6.2%), junenol (< or = 6.1%) and alpha- or beta-pinene (< or = 5.5%). Eighty-seven compounds were identified, comprising 73.6-92.3% of the oils. The chemical composition was highly variable depending on the sample location. Toxicity of A. campestris oils was determined using the brine shrimp (Artemia sp.) assay. LC50 values ranging to 20 microg/mL were obtained for three of the oils after 24 hours of exposure. Data of this test revealed that A. campestris ssp. campestris essential oils with dominant caryophyllene oxide are notably toxic.

Analysis of essential oils of Artemisia absinthium L. from Lithuania by CC, GC(RI), GC-MS and 13C NMR.

Different techniques have been utilized to determine the composition of Artemisia absinthum (wormwood) essential oil. The oil was fractionated on a silica gel column and each fraction analyzed by GC(RI), GC-MS and 13C NMR. This allowed the identification, for the first time in A. absinthium, of two diterpenes, 9-geranyl-p-cymene and 9-geranyl-alpha-terpinene, and two homoditerpenes, 9-(15,16-dihydro-15-methylene)-geranyl-p-cymene and 9-(15,16-dihydro-15-methylene)-geranyl-alpha-terpinene. Chemical variability of A. absinthium essential oils from plants collected in the surroundings of Vilnius city over several years (1999-2007) was also shown. Chemical composition was determined by GC and GC-MS. Thujones (cis+trans, 10.2-36.3%) and trans-sabinyl acetate (9.8-39.2%) were the two predominant constituents of almost all the investigated oils (13 out of 15 samples). The third major compound was myrcene (5.1-9.2%, in four samples), beta-pinene (5.4-10.4%, in 5), linalool (4.7% in one), trans-sabinol (6.4%, in one) and 1,8-cineole (5.2-7.1%, in two). In one oil, the prevailing components were thujones (cis+trans, 11.2%), trans-sabinene hydrate (11.0%) and trans-sabinyl acetate (8.8%), while another sample was characterized by a large quantity of trans-sabinyl acetate (55.2%) and the absence of thujones.

The essential oil qualitative and quantitative composition in the needles of Pinus sylvestris L. growing along industrial transects.

The aim of this study was to evaluate composition of the essential oils in the needles of Pinus sylvestris growing in the areas affected by a cement factory (CF), and an oil refinery (OR). Volatile components of the needles were analyzed by GC and GC/MS. The most heavily polluted CF stand had significantly higher concentration of gamma-Terpinene, Caryophyllene oxide in the current-year needles, while higher concentration of delta-3-Carene, alpha-Terpinene, gamma-Terpinene and Terpinolene was documented for 1-year-old needles. The most heavily polluted OR stand had a significantly higher concentration of Sabinene+beta-Pinene, 1-epi-Cubenol in the current-year needles and a significantly higher concentration of Camphene, Sabinene+beta-Pinene, Myrcene, alpha-Cadinene, 1-epi-Cubenol in the 1-year-old needles than the least polluted site. Along transects an increase in the amount of some diterpenes and a decrease in the components of the shorter chain essential oils was observed. These effects could be at least partially attributed to SO(2).

Changes in the essential oil composition in the needles of Scots pine (Pinus sylvestris L.) under anthropogenic stress.

Unfavorable anthropogenic factors, such as air pollution, lead to biochemical responses in trees. Changes in the amounts of secondary metabolites may be early indicators of invisible injuries. The aim of this study was to evaluate composition of the essential oils in the needles of Scots pine (Pinus sylvestris L.) growing in the areas affected by pollutant emissions of main factories in Lithuania: a nitrogen fertilizer factory (NFF), a cement factory (CF), and an oil refinery (OR). Totally, 14 pine stands were examined along transects from the factories (July 2005). Volatile components of the needles were extracted and analyzed by GC and GC/MS. Over 70 components of the essential oils were identified in current-year and 1-year-old needles. Along the CF transect for current-year needles, the percentage of diterpenes was decreasing with the increasing pH of the pine bark (r = -0.582; p < 0.05) or with the increasing concentration of SO2 (r = -0.573; p < 0.05); for 1-year-old needles, the percentage of diterpenes was decreasing with the increasing pH of the bark (r = -0.534; p < 0.05). Along the OR transect, in both the current-year and 1-year-old needles, the percentage of diterpenes was decreasing with the increasing SO2 (respectively, r = -0.773; p < 0.01; r = -0.486; p < 0.05); an opposite relation was true for sesquiterpenes (respectively, r = -0.751; p < 0.01; r = 0.785; p < 0.01). The view was different along the NFF transect. For current-year needles, the percentage of monoterpenes was decreasing with the increasing NH3 (r = -0.669; p < 0.01); while the percentage of sesquiterpenes or oxysesquiterpenes was increasing with the increasing NH3 (respectively, r = 0.540; p < 0.05 and r = 0.688; p < 0.01). For each transect, cluster analysis of the percentages of components of essential oils in the needles allowed us to distinguish the most contrasting stands according to the concentration of air pollutants. Current-year needles were more effective as indicators of the effects of pollution than 1-year-old needles in the case of the NFF and the OR transects, and both-aged needles were equally valuable in the case of the CF transect. The changes detected in the proportions of components of the essential oils in the needles of the trees affected by the industrial emissions may play a significant role in modifying the susceptibility of the pine stands to the biotic factors, and also may alter emissions of terpenes from the stands to the atmosphere.