Diterpenoid acids from <Emphasis Type="Italic">Pinus koraiensis</Emphasis>

Two new diterpenoid acids, pinusenocarp (1) and pinusenoid (2), were isolated from the pine cone of Pinus koraiensis. All the compounds were characterized on the basis of spectral analysis, viz. ¹H NMR, ¹³C NMR, IR, UV, ESI-MS, and elemental analysis.     

Determination of polycyclic aromatic hydrocarbons in the needles of a Scotch pine (<Emphasis Type="Italic">Pinus sylvestris</Emphasis> L.), a biomonitor of atmospheric pollution

A procedure was developed for the determination of polycyclic aromatic hydrocarbons (PAH) in the needles of a Scotch pine (Pinus sylvestris L.), which is characterized by the simple and efficient sample preparation. The procedure involves the steps of the extraction of PAH with n-hexane on ultrasonic irradiation, the precipitation of concomitant cereous components from the extract on its cooling, the purification of the PAH fraction on a cartridge with silica gel (0.5 g), and the redissolution of the concentrated eluate in methanol. The quantitative determination of PAH (15 compounds including 13 priority) with the use of chromatography-mass spectrometry in the selective ion detection mode exhibits the interlaboratory precision of the results of the PAH determination V _Rl = 0.059–0.088 for the concentration of PAH in needles from 0.3 to 600 ng/g and a detection limit of 0.06 ng/g (signal-to-noise ratio = 3; mass of the sample for extraction was 10 g). The accumulation levels of PAH in the Scotch pine needles were presented; the needles were first studied as a biomonitor of atmospheric pollution over the southern part of the Baikal natural territory.     

Gas-liquid chromatographic separation of common amino acids in pine needle extracts

An improved gas—liquid chromatographic method based on the separation of N-trifluoroacetyl n-butyl esters of amino acids on a “two-column” setup --- Tabsorb and Tabsorb HAC --- was developed for the identification and estimation of amino acids in pine needles (Pinus banksiana Lamb.). A comparative study was made of various available gas—liquid chromatographic methods for separation and estimation of amino acids from pine needle extracts.     

Comparison of PAH Levels and Sources in Pine Needles from Portugal,Spain, and Greece

The main objective of this work was to assess and compare the levels, patterns, and sources of contamination of 16 polycyclic aromatic hydrocarbons (PAHs) between Portugal, Spain, and Greece (in the island of Crete). A total of 9 sampling sites were chosen (4 in urban and 5 in non-urban areas) in each country and pine needles from the Pinus pinea L. species were collected. Although the mean total PAH levels was similar in the three countries (279 ± 236 ng g^?1 for Portugal, 294 ± 258 ng g^?1 for Spain, 301 ± 253 ng g^?1 for Greece, all dry weight) and, in general, 3-ring and 4-ring PAHs were predominant (being phenanthrene consistently the most abundant), there were some visible differences in the aromatic ring patterns and possible sources between the three regions. Source apportionment was done using PAH ratios (Phen/Ant and Flt/Pyr crossplots) and reflected mixed petrogenic and pyrogenic sources. Furthermore, Principal Component Analysis (PCA) clearly separated the urban and the non-urban sites and all three countries, which reinforces that the sources of contaminations vary in each case and the suitability of pine needles for trans-boundary biomonitoring of PAHs.     

Accumulation of Major,Minor and Trace Elements in Pine Needles (Pinus nigra) in Vienna (Austria)

Increasing heavy metal pollution in the environment and the fact that pine needles are good bio-monitors for air pollutants was the reason to investigate their accumulation in pine needles in Vienna (Austria). Pinus nigra is widespread over the city, thus allowing the study of different parameters influencing metal accumulation. The sampling sites were chosen based on traffic volume (low, medium, high). Fresh shoots were collected alongside one-year-old needles once per week from May to August 2015. The needle samples were washed and dried prior to acidic microwave-assisted digestion followed by quantitative determination using spectrometric methods. The investigation was focused on the following elements: Ag, Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Se, Sr, U, V, and Zn. The one-year-old needles mainly contained higher contents of elements than fresh shoots; in many cases, the values differed statistically significantly. By correlating needle elemental contents with the sampling site, statistically significant differences were registered for the majority of the investigated elements. These differences originate from the local traffic situation, soil elemental levels, translocation processes, and not traffic-related sources. No general trend of metal accumulation from spring to summer was registered.     

Multielemental Analysis of Yew,Pine and Spruce Needles by ICP-AES

Abstract

Concentrations of 22 trace and nutritional elements in yew, pine and spruce needles collected from urban and industrial areas were determined by inductively coupled plasma atomic emission spectrometry. Dependence of concentrations of trace elements in conifers species on sampling site was investigated. Various procedures of sample digestion (different acids, conventional hot plate and microwave digestion methods, dry ashing) were examined and discussed.     

Characterization and sources of extractable organochlorine in white sucker downstream from bleached kraft pulp mills

Organochlorine, obtained by extraction with hexane–acetone mixture (3?:?1) of fillets of white sucker (Catostomus commersoni) sampled downstream of pulp mills and in a reference river, was characterized by gel-permeation chromatography, transesterification, neutron activation analysis, and gas chromatography with halogen-sensitive detection. It was found that over 78% of the extractable organochlorine (EOCl) is of relatively high molecular weight (>～350). Chlorinated fatty acids account for 43–80% of EOCl in the high-molecular-weight portion, while chlorobenzenes, chlorinated pesticides, and polychlorinated biphenyls account for 4–55% of EOCl in the low-molecular-weight portion. Though undetectable in reference fish, three particular chlorinated fatty acids, i.e. threo-5,6-dichlorotetradecanoic, threo-7,8-dichlorohexadecanoic and threo-9,10-dichlorooctadecanoic acids, are characteristic of EOCl from fish collected downstream of bleached kraft pulp mills using chlorine-based bleaching, representing about 30% of total EOCl, of which threo-5,6-dichlorotetradecanoic acid alone accounts for 60–70%. It is thus evident that, among chlorinated compounds discharged from bleached kraft pulp mills, threo-9,10-dichlorooctadecanoic acid, presumably generated in chlorine-based bleaching processes, is the most bio-accumulative in fish and can be biodegraded by fish into dichlorohexadecanoic and dichlorotetradecanoic acids, presumably via β-oxidative metabolism. These three compounds were also identified in suspended solids isolated from biologically treated final effluent discharged from a bleached pulp mill using 50% ClO₂ substitution, thus confirming the effluent-related source for downstream fish. The finding also suggests that β-oxidation of dichlorooctadecanoic acid may also be operative in micro-organisms.     

Two new myricetin glycosides from pine needles of <Emphasis Type="Italic">Cedrus deodara</Emphasis>

Two new myricetin glycosides, myricetin-3-O-(6″-O-E-p-coumaroyl)-α-D-glucocopyranoside (1) and 3′,5′-di-O-methylmyricetin-3-O-(6″-O-acetyl)-α-D-glucopyranoside (2), and three known flavonoids, myricetin (3), cedrin (4), and 2R,3R-dihydromyricetin (5), were isolated from the pine needles of Cedrus deodara. Their structures were elucidated on the basis of extensive spectroscopic analysis and chemical evidence.     

广西产马尾松与湿地松针叶精油化学成分的比较

用水蒸气蒸馏法从广西产马尾松和湿地松的针叶中提取精油,探索了松针投料量和提取时间对产油率的影响,确定了最佳工艺条件为：松针投料量700 g,提取时间5 h。在此最佳条件下马尾松和湿地松针叶的产油率分别为0.45%和0.19%。用气相色谱（GC）和气相色谱-质谱（GC-MS）等方法分别对两树种的针叶精油进行了定量和定性分析,从马尾松针叶精油中分离出64种化学成分,鉴定了其中的20种成分,占挥发油总量的98.59%;从湿地松针叶精油中分离出73种化学成分,鉴定了其中的29种成分,占挥发油总量的94.23%。两树种针叶精油的主要化学成分大致相同,但在含量上有较大差别。马尾松针叶精油中α-蒎烯的含量约为湿地松的2.6倍,但其β-蒎烯含量低于后者。单萜和倍半萜是构成马尾松和湿地松针叶精油的主要成分。     

Microwave-assisted extraction and ultrasonic extraction to determine polycyclic aromatic hydrocarbons in needles and bark of Pinus pinaster Ait. and Pinus pinea L. by GC-MS

Two different extraction strategies (microwave-assisted extraction (MAE) and ultrasonic extraction (USE)) were tested in the extraction of the 16 US Environmental Protection Agency (EPA) polycyclic aromatic hydrocarbons (PAHs) from pine trees. Extraction of needles and bark from two pine species common in the Iberian Peninsula (Pinus pinaster Ait. and Pinus pinea L.) was optimized using two amounts of sample (1 g and 5 g) and two PAHs spiking levels (20 ng/g and 100 ng/g). In all cases, the clean-up procedure following extraction consisted in solid-phase extraction (SPE) with alumina cartridges. Quantification was done by gas chromatography (GC) with mass spectrometry (MS), using five deuterated PAH surrogate standards as internal standards. Limits of detection were globally below 0.2 ng/g. The method was robust for the matrices studied regardless of the extraction procedures. Recovery values between 70 and 130% were reached in most cases, except for high molecular weight PAHs (indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[ghi]perylene). A field study with naturally contaminated samples from eight sites (four in Portugal and four in Catalonia, Spain) showed that needles are more suitable biomonitors for PAHs, yielding concentrations from 2 to 17 times higher than those found in bark. The levels varied according to the sampling site, with the sum of the individual PAH concentrations between 213 and 1773 ng/g (dry weight). Phenanthrene was the most abundant PAH, followed by fluoranthene, naphthalene and pyrene.     

Supercritical fluid extraction as a tool for isolation of monoterpenes from coniferous needles and walnut-tree leaves

Several monoterpenes, i.e., (+)-α-pinene, (−)-camphene, sabinene, (−)-β-pinene, myrcene, R-(+)-limonene, (−)-bornylacetate, (−)-trans-caryophyllene and a-humulene were identified and determined by gas chromatography-mass spectrometry (GC-MS) in needles of Pinaceae (Picea abies, P. omorika, P. pungens, P. Breweriana, Pinus nigra, P. mungo turra, P. black, P. sylvestris, Abies pinsapo, A. holophylla, A. Bronmuelleris, A. alba, Larix Kaempferi L. decidua) and tree-leaves of Juglandaceae (Juglans regia, J. nigra, J. sieboldiana var. Cordiformis) families. Supercritical fluid extraction (SFE) was found to be very useful for their isolation at optimised conditions (needles/leaves: pressure 20/30 MPa, temperature 80/130°C, time of extraction 60/60 min, modifier chloroform/chloroform). Their seasonal distribution, evaluation of differences in concentrations and relative amounts in different trees and their varieties grown in different localities were evaluated.      

Examination of the lignin content in a softwood and a hardwood decayed by a brown‐rot fungus with the acetyl bromide method and Fourier transform infrared spectroscopy

Fourier transform infrared (FTIR) spectroscopy was used to examine lignin modification in Pinus sylvestris L. (Scots pine) and Fagus sylvatica L. (beech) decayed to different weight losses by the brown‐rot fungus Coniophora puteana. Samples of different weight losses, ranging from 3 to 64% for beech and 15 to 62% for pine, were analyzed along with undecayed controls. The ratios of the heights of the lignin/carbohydrate FTIR peaks were determined, and the lignin contents of the blocks were measured with the acetyl bromide method. The ratios of the reference peaks for lignin against polysaccharide (i.e., cellulose and hemicellulose) peaks were compared with the lignin content of the wood determined by the acetyl bromide method. A good correlation was obtained for ratios of some of the lignin/carbohydrate reference peaks (lignin peaks at 1505 and 1330 cm^?1 for beech and at 1511 and 1225 cm^?1 for pine against polysaccharide peaks at 1734, 1375, and 1158 cm^?1) against the lignin content for both wood species decayed to different levels. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2340–2346, 2004     

The effects of α-cellulose extraction and blue-stain fungus on retrospective studies of carbon and oxygen isotope variation in live and dead trees

Tree‐ring carbon and oxygen isotope ratios from live and recently dead trees may reveal important mechanisms of tree mortality. However, wood decay in dead trees may alter the δ¹³C and δ¹⁸O values of whole wood obscuring the isotopic signal associated with factors leading up to and including physiological death. We examined whole sapwood and α‐cellulose from live and dead specimens of ponderosa pine (Pinus ponderosa), one‐seed juniper (Juniperous monosperma), piñon pine (Pinus edulis) and white fir (Abies concolor), including those with fungal growth and beetle frass in the wood, to determine if α‐cellulose extraction is necessary for the accurate interpretation of isotopic compositions in the dead trees. We found that the offset between the δ¹³C or δ¹⁸O values of α‐cellulose and whole wood was the same for both live and dead trees across a large range of inter‐annual and regional climate differences. The method of α‐cellulose extraction, whether Leavitt‐Danzer or Standard Brendel modified for small samples, imparts significant differences in the δ¹³C (up to 0.4‰) and δ¹⁸O (up to 1.2‰) of α‐cellulose, as reported by other studies. There was no effect of beetle frass or blue‐stain fungus (Ophiostoma) on the δ¹³C and δ¹⁸O of whole wood or α‐cellulose. The relationships between whole wood and α‐cellulose δ¹³C for ponderosa, piñon and juniper yielded slopes of ~1, while the relationship between δ¹⁸O of whole wood and α‐cellulose was less clear. We conclude that there are few analytical or sampling obstacles to retrospective studies of isotopic patterns of tree mortality in forests of the western United States. Published in 2011 by John Wiley & Sons, Ltd.     

Headspace-single drop microextraction (HS-SDME) in combination with high-performance liquid chromatography (HPLC) to evaluate the content of alkyl- and methoxy-phenolic compounds in biomass smoke

The content of ten phenolic compounds present in four different biomass smoke materials: rock rose (Cistus monpelienisis), prickly pear (Opuntia ficus indica), pine needles (Pinus canariensis), and almonds skin (Prunus dulcis), have been evaluated. The sampling method mainly consisted of a trap alkaline solution to solubilize the phenols, and was optimized by an experimental design. Average sampling efficiencies of 78.1% and an average precision value of 10.6% (as relative standard deviation, RSD), were obtained for the selected group of phenols. The trapped phenolates were further analyzed by a headspace-single drop microextraction (HS-SDME) procedure, in combination with high-performance liquid chromatography (HPLC) with UV detection. The optimum variables for the HS-SDME method were: 1-decanol as extractant solvent, 3.5 μL of microdrop volume, 2 mL of sample volume, a pH value of 2, saturation of NaCl, an extraction temperature of 60 °C, and an extraction time of 25 min. The optimized HS-SDME method presented detection limits ranging from 0.35 to 5.8 μg mL⁻¹, RSD values ranging from 0.7 to 7.4%, and an average relative recovery (RR) of 99.8% and an average standard deviation of 5.2. The average content of phenolic compounds in the biomass materials studied were 70, 161, 206 and 252 mg kg⁻¹ of biomass for prickly pear, almonds skin, rock rose, and pine needles, respectively. The main components of the smokes were vanillin, phenol and methoxyphenols, in all smoking materials studied.     

Sustainable natural adsorbents for heavy metal removal from wastewater: lead sorption on pine bark (Pinus radiata D.Don)

Aqueous Pb(II) adsorption on pine bark (Pinus Radiata D.Don), an inexpensive and sustainable natural sorbent material, has been evaluated and the mechanism of metal retention characterized by scanning electron microscopy (SEM), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X‐ray photoelectron spectroscopy (XPS). Bark pulp densities >1.5 g l^?1 achieve near 100% Pb(II) removal from aqueous solutions containing 100 mg l^?1 Pb(II). Adsorption rates increased with pulp density, although adsorption capacity diminished at high densities because of blockage of adsorption sites. The effects of washing and sulfuric acid activation were assessed and found to be less important than in previous metal sorption studies. Pb(II) sorption takes place mainly at the lignocellulosic C―O groups, with adsorption at phenolic sites appearing to be most significant. © 2016 The Authors. Surface and Interface Analysis published by John Wiley & Sons, Ltd.     

Three new sulphur glycosides from the seeds of Descurainia sophia

Three new sulphur glycosides, raphanuside B–D (1–3), together with a known sulphur glycoside, raphanuside (4) were isolated from the decoction of the seeds of Descurainia sophia (L.) Webb ex Prantl, and the compound 4 was reported for the first time from this plant. Their structures were identified by means of UV, IR, 1D, 2D NMR (HSQC, HMBC and NOESY) and HR–ESI–MS spectroscopic data.     

Changes in the composition of volatile monoterpenes and sesquiterpenes of Pinus armandi, P. tabulaeformis, and P. bungeana in Northwest China

The volatile mono-and sesquiterpenes obtained from the needles and resin of Pinus armandi, P. tabulaeformis, and P. bungeana growing in the Qinling, Taibai, and Huanglong Mountain forest ecosystem were analyzed by means of GC-MS. Forty-eight constituents were identified, and α-pinene, β-pinene, 1R-α-pinene, β-caryophyllene, cadindiene, α-caryophyllene, D-limonene, and 1S-β-pinene were the major components of the mono-and sesquiterpenes in the needles and resin. The components of the volatile mono-and sesquiterpenes from the needles and resin at Qinling, Taibai, and Huanglong Mountains had remarkable differences in three pine species, whereas the monopertene content such as α-pinene, β-pinene, D-limonene, and camphene were mostly changed in the growing stage. The intraspecies variation in the different ecosystems can be attributed to the species’ geography and genetic variation, and even the adaptation of the pine species to different ecological environments. Moreover, monoterpenes and sesquiterpenes can be induced by the attack of bark beetles, of which the α-pinene, β-pinene, 1R-α-pinene, 1S-α-pinene, b-myrecene, and β-caryophyllene contents had positive relations with the attacking Dendroctonus armandi and D. valens. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 430–433, September–October, 2006.     

Seasonal variations of radionuclide concentrations in pine needles

Seasonal variations of radionuclide concentration in pine needles (Pinus Thunbergii) were examined. The seasonal variations were classified roughly into two types, one represented by the periodical variation of¹³⁷Cs concentration and the other represented by a linear decrease of¹⁰³Ru concentration when plotted on a semi-log scale. Weathering half-lives for the latter type of nuclides were estimated and a fairly good consistency in the half-lives for different nuclides was observed irrelevant to their radioactive half-lives.     

利用甾体皂甙元氧化降解废弃物(R)-4-甲基-δ-戊内酯合成松叶蜂主要性信息素(2S,3S,7S)-3,7-二甲基-2-十五醇乙酸酯和丙酸酯

首次利用甾体皂甙元氧化降解废弃物(R)-4-甲基-δ-戊内酯合成了松叶蜂性信息素(2S,3S,7S)-3,7-二甲基-2-十五醇乙酸酯(2)和丙酸酯(3). 甾体皂甙元氧化降解废弃物(R)-4-甲基-δ-戊内酯首先被转化成为性质稳定易保存的(R)-5-溴-4-甲基戊酸甲酯(5), 化合物5经过偶联、还原、溴代、环氧加成开环和酰化反应给出目标分子. 本研究结果不仅为松叶蜂性信息素化合物2和3提供了一个简洁有效的合成方法, 同时也丰富了资源化学(即基于资源性化合物合理利用的有机合成化学)的内涵.     

火焰原子吸收光谱法测定红松松针中微量元素含量

采用火焰原子吸收光谱法测定了长白山红松松针中K、Ca、Mg、Zn、Cu、Fe和Mn 7种金属元素含量。结果表明,在常量元素中K、Ca含量较高,微量元素中Fe、Zn含量较高,7种金属元素含量由高到低顺序分别为:K、Ca、Fe、Mg、Zn、Mn、Cu。可见松针中含有丰富的与健康密切相关的微量元素,具有较高的食用和药用价值。