Tissue free water tritium in pine needles around a nuclear power plant

The elevation of the concentration of tissue free water tritium (TFWT) in pine needles was discernible in trees growing around a nuclear power plant. The values varied from 2.6 Bq/l to 6.1 Bq/l with a mean value of 3.8 Bq/l. Analysis of pine needles collected at Fukui City as control samples was done. The values averaged 1.7 Bq/l and fell within 1.5 B/l-1.8 Bq/l which was obtained nation-wide survey of TFWT in pine needles in Japan. The present study also revealed that reactor tritium incorporated into pine needles decreased rapidly with a half time of 6 days and then tissue free water tritium has a short retention time.     

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.     

Investigation and isolation of a protein-vitamin concentrate from pine needles

Summary 1. The fractional and amino-acid compositions of needle proteins and of a protein-vitamin concentrate isolated from an extract have been determined.2. The optimum conditions of the protein-extracting process have been found. The dependence of the influence of various factors on the degree of extraction of the protein from the needles has been shown.3. The results obtained enable the protein-vitamin concentrate to be recommended as a valuable additive to fodder for agricultural animals.Siberian Technological Institute, Krasnoyarsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 517–522, July–August, 1976.     

Temporal variation of tritium concentration in tree-ring cellulose

Tritium concentration of organically bound hydrogen has been measured during the 1941 to 1987 period using a cellulose fraction extracted from pine tree grown in Tatsunokuchi-machi, Ishikawa Prefecture, Japan. It was concluded that most of the tritium bound in cellulose was supplied from the mixture of underground water in the root zone of the pine tree. Underground water was strongly influenced by the precipitation and waters with different residence times. This revised version was published online in July 2006 with corrections to the Cover Date.     

Monitoring polychlorinated biphenyls in pine needles using supercritical fluid extraction as a pretreatment method

This paper reports on the first use of supercritical fluid extraction (SFE) of polychlorinated biphenyls (PCBs) from pine needles. Supercritical carbon dioxide was used as extraction fluid, and exhibited good extraction efficiencies and recoveries (>90%). GC-MS (selected ion monitoring mode) achieved both accurate identification and quantification of the PCBs. Compared with traditional time consuming multi-step sample preparation methods, SFE with carbon dioxide is easier to perform, and is a feasible alternative extraction procedure for the monitoring of PCBs in pine needle samples.     

Levels of tritium concentration in the environmental samples around JAERI TOKAI

By the operation of research reactors, tritium-handling facilities, nuclear power plants, and a reprocessing facility around JAERI TOKAI, tritium is released into the environment in compliance with the regulatory standards.To investigate the levels of tritium concentration in environmental samples around JAERI, rain, air (vapor and hydrogen gas), and tissue-free water of pine needles were measured and analyzed from 1984 to 1993. Sampling locations were determined by taking into consideration wind direction, distance from nuclear facilities, and population distribution. The NAKA site (about 6 km west-northwest from the TOKAI site) was also selected as a reference point.Rain and tissue-free water of pine needles were sampled monthly. For air samples, sampling was carried out for two weeks by using the continuous tritium sampler. After the pretreatment of samples, tritium concentrations were measured by a low background liquid scintillation counter (detection limit is 0.8 Bq/l).Annual mean tritium concentrations in rain observed at six points for 10 years was 0.8 to 8.9 Bq/l, which decreased with distance from the nuclear facilities. Tritium concentrations in rain obtained at Chiba City were around 0.8 Bq/l (1987–1988) and those at the NAKA site were 0.8 to 3.8 Bq/l.Annual mean HTO concentrations in air at three points for 10 years were 9.2×10^–2 to 1.1 Bq/m³, although HT concentrations in air, ranging from 1.7×10^–2 to 5.8×10^–2 Bq/m³, were not influenced by the operation of the nuclear facilities.Annual mean tritium concentrations in tissue-free water of pine needles at four points for 10 years were 1.4 to 31 Bq/l. Those at the NAKA site ranging from 1.4 to 6.2 Bq/l were in good agreement with the reported value by Takashima of 0.78 to 3.0 Bq/l at twenty-one locations in Japan.Monthly mean HTO concentrations in air for 10 years showed a good correlation with absolute humidity, while other samples showed no seasonal variation.Higher level tritium concentrations in rain, in air (vapor), and in tissue-free water of pine needles at the TOKAI site were caused by the tritium released from the nuclear facilities.The committed effective dose equivalent to the member of general public, estimated using the maximum tritium concentration in air (1.1 Bq/m³), was 0.23 Sv, which was about 1/4000 of dose limit for general public.     

An analytical multi-residue approach for the determination of semi-volatile organic pollutants in pine needles

Vegetation (and pine needles in particular) has been widely used as an alternative to other conventional sampling devices to assess the atmospheric presence of semi-volatile organic contaminants (SVOCs). While most analytical procedures developed focus only on one or two chemical classes, this this work intends to establish a multi-component protocol to quantify brominated flame-retardants (BFRs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polynuclear aromatic hydrocarbons (PAHs) and one class of contaminant of emerging concern, the synthetic musks fragrances (SMCs). Pine needles extracts were obtained by ultrasonic solvents extraction (USE), and different cleanup approaches using solid-phase extraction (SPE) employing combinations of sorbents and solvents as well as gel permeation chromatography (GPC) were tested. SPE with alumina followed by GCP yielded the best results, with average recoveries over 80%.     

高效液相色谱法测定松针中莽草酸的含量

松针为我国传统中药,<本草纲目>曰:松针,味苦温、无毒,久服令人不老,轻身益气,主治风湿疮,生毛发,安五脏,守中,不饥,延年[1].历代均入药用,民间用于治疗神经衰弱、维生素丙缺乏症、营养性水肿、风牙肿痛、阴囊湿痒、腰痛、跌打损伤和预防钩虫病[2].现代临床医学上常用以治疗慢性气管炎、预防流脑和感冒.     

Development of non-destructive methods for the determination of airborne pollutants in pine needles: identification of trace constituents in radiata pine epicuticular wax

Summary In an attempt to develop non-destructive work-up procedures for monitoring lipophilic pollutants in the air by analysis of pine needle epicuticular wax, a project was undertaken to identify substances that interfere with the normal gas-chromatographic quantitations. Epicuticular wax was extracted from needles of radiata pine and processed to remove the bulk estolides and resin and fatty acids. Fractionation of the residue on a silica gel column gave three fractions, representing less than 0.2% of the wax. The fractions contained a mixture of natural products and anthropogenic chemicals. Among the natural products were sesquiterpenes, comprising mainly amorphene, cadinenes, germacrene and cadalene; bisnor-, nor- and diterpene hydrocarbons; methyl esters of resin acids; and 9,10-secodehydroabietanes of unknown ring-A structure. Some of these compounds have not been reported from pine needle epicuticular wax previously. Anthropogenic chemicals identified include polycyclic aromatic hydrocarbons. The organochlorine compounds of environmental importance were hexachloro-cyclohexanes (including lindane), hexachlorobenzene, pentachloroanisole, chlordanes, dieldrin, p,p-DDE, p,p-DDT, and penta-, hexa- and heptachlorobiphenyls. The organochlorine compounds were present at concentration orders of magnitude lower than the interfering compounds, and therefore had to be identified using gas chromatography-mass spectrometry methods. By identifying the interfering compounds, non-destructive work-up procedures could be developed in order to retain the integrity of all of the anthropogenic compounds contributing to environmental pollution.     

Temporal variation of tritium concentration in tree-ring cellulose over the past 50 years

Concentration of organically-bound tritium in the tree-ring cellulose of a pine tree grown in Shika-machi, Ishikawa prefecture, Japan (37.1°N, 136.5°E), was measured during the ring-years from 1949 to 1999. The results were compared with those of a pine tree grown in Tatsunokuchi-machi, Ishikawa prefecture, Japan (36.4°N, 136.5° E). The annual variation of tritium in tree rings demonstrated two differences between the Shika-machi tree and the Tatsunokuchi-machi tree. No secondary peak appeared in the period after the maximum peak of 1963 for the Shika-machi tree, while two peaks appeared in 1966 and 1970 for the Tatsunokuchi-machi tree. In addition, the height of the 1963 peak was 30% higher for the Shika-machi tree than for the Tatsunokuchi-machi tree. These differences are considered to be caused by the influence that the underground water in the root zone of the Tatsunokuchi-machi tree was strongly affected by water which was transported to the tree site from mountain regions as compared to the Shika-machi tree.This study was supported in part by a Grant from the Ishikawa Prefectural Institute of Public Health and Environmental Science.     

Temporal variation of tritium concentration in tree-ring cellulose over the past 50 years

Concentration of organically-bound tritium in the tree-ring cellulose of a pine tree grown in Shika-machi, Ishikawa prefecture, Japan (37.1°N, 136.5°E), was measured during the ring-years from 1949 to 1999. The results were compared with those of a pine tree grown in Tatsunokuchi-machi, Ishikawa prefecture, Japan (36.4°N, 136.5° E). The annual variation of tritium in tree rings demonstrated two differences between the Shika-machi tree and the Tatsunokuchi-machi tree. No secondary peak appeared in the period after the maximum peak of 1963 for the Shika-machi tree, while two peaks appeared in 1966 and 1970 for the Tatsunokuchi-machi tree. In addition, the height of the 1963 peak was 30% higher for the Shika-machi tree than for the Tatsunokuchi-machi tree. These differences are considered to be caused by the influence that the underground water in the root zone of the Tatsunokuchi-machi tree was strongly affected by water which was transported to the tree site from mountain regions as compared to the Shika-machi tree.This study was supported in part by a Grant from the Ishikawa Prefectural Institute of Public Health and Environmental Science.     

Hollow-fibre liquid-phase microextraction: a simple and fast cleanup step used for PAHs determination in pine needles

A new, fast and simple cleanup procedure, based on hollow-fibre liquid-phase microextraction (HF-LPME) is described here, used for the determination of 13 polycyclic aromatic hydrocarbons (PAHs) in complex pine needle samples. Initially, pine needle samples were sonicated in a 20 mL aqueous solution having a 20% (v:v) acetone content and 5 mL of the sonicated liquid extract was then used for the HF-LPME cleanup step. Different experimental parameters (namely: type of organic solvent used as acceptor phase, effect and type of co-solvent, salt addition, sample agitation and sampling time) were controlled and optimized based on the response of GC-MS instrument under the SIM mode. Under the optimized experimental conditions found the typical chromatograms obtained revealed that despite the very complex matrix of pine needles the HF-LPME cleanup step greatly reduced if not eliminated the presence of interferents, resulting in chromatograms which contained very cleanly separated and readily evaluable PAH peaks. In addition, the proposed method was found to be linear in the concentration 10-2000 ng g⁻¹ for most target analytes and the limits of detection for a S/N = 3 ranged between 0.01 and 0.95 ng g⁻¹ (dry weight). Furthermore, the repeatability and reproducibility were also found good. Finally, the proposed method was applied for the analysis of real pine needle samples taken for different parts of the island of Crete.     

Pyrolysis of pine needles: effects of process parameters on products yield and analysis of products

Pyrolysis of pine needles was carried out in a semi-batch reactor. The effects of pyrolysis parameters such as temperature (350–650 °C), heating rate (10 and 50 °C min^?1), nitrogen flow rate (50–200 cm³ min^?1) and biomass particle size (0.25–1.7 mm) were examined on products yield. Maximum bio-oil yield of 43.76% was obtained at pyrolysis temperature of 550 °C with a heating rate of 50 °C min^?1, nitrogen flow rate of 100 cm³ min^?1 for biomass particle size of 0.6 < d _p < 1 mm. The characterization of pyrolysis products (bio-oil, bio-char) has been made through different instrumental methods like Fourier transform infrared spectroscopy, gas chromatography–mass spectrometry, nuclear magnetic resonance spectroscopy (¹H NMR), X-ray powder diffraction, field emission scanning electron microscope and Brunauer–Emmett–Teller surface area analysis. The empirical formula of the bio-oil and bio-char was found as CH_1.47O_0.36N_0.005 and CH_0.56O_0.28N_0.013 with heating value of 26.25 and 25.50 MJ kg^?1, respectively. Results show that bio-oil can be potentially valuable as a renewable fuel after upgrading and can be used as a feedstock for valuable chemicals production. The properties of bio-char reveal that it can be used as solid fuels, as a cheap adsorbent and as a feedstock for activated carbon production.     

Variation of atmospheric tritium concentrations in three different chemical forms in Fukuoka, Japan

Atmospheric tritium concentrations of tritiated water vapor (HTO), tritiated hydrogen (HT) and tritiated hydrocarbons (primarily tritiated methane, CH₃T) have been measured in Fukuoka prefecture, Japan from 1984 to the present to establish a general database on the behavior of atmospheric tritium. HTO concentrations expressed in Bq/l-H₂O vary within a range of 1.19 to 2.45, giving an overall average value of 1.86±0.077. HTO concentrations expressed in-mBq/m³-air vary within a range of 7.8 to 46.1 and have a strong correlation with the atmospheric humidity, being high in the summer and low in winter. In the case of HT and CH₃T, no seasonal variations were observed with average monthly values of 23.1 to 61.0 mBq/m³-air and 8.3 to 23.9 mBq/m³-air, respectively. The present HTO concentrations are already close to the tritium level before nuclear testings. However, the present HT and CH₃T concentrations are still higher by a factor of about 140 and 30, respectively, than those before the testings. Specific activities are estimated to be 14.6–16.7 TU for HTO, 5.5·10⁵–1.0·10⁶ TU for HT and 3.2·10⁴–4·10⁴ TU for CH₃T. The apparent difference in the specific activities suggests a very slow transformation of these species in the atmosphere or a continuous supply of HT and CH₃T with high specific activity. Residence time for atmospheric HT was found to be 6.5 years over the period 1988–92 and 10 years for 1988–95. These times are longer than 4.8 years given by Mason and Östlund in the 1970s, and thus indicate a supply to the atmosphere of HT from various tritium sources.     

Determination of optimum conditions for the analysis of volatile components in pine needles by double-shot pyrolysis-gas chromatography-mass spectrometry

The optimum conditions for the analysis of the volatile organic components of pine needles from Pinus densiflora using double-shot pyrolysis-gas chromatography-mass spectrometry (DSP-GC-MS) were investigated with respect to thermal desorption temperature and duration of heating. A total of 41 compounds were identified using thermal desorption temperatures of 150 degrees C, 200 degrees C, 250 degrees C and 300 degrees C. Thermal decomposition products, which include acetol, acetic acid, furfurals and phenols, were observed only at thermal desorption temperatures exceeding 250 degrees C: they were not observed in the extract from a simultaneous distillation extraction (SDE) method. Heating times of 1 s, 6 s, 30 s, 150 s and 300 s were investigated at the thermal desorption temperature of 200 degrees C, whence it was found that thermal decomposition products were produced only at heating times over 30 s. The optimum pyrolyzer conditions for the analysis of pine needles using DSP-GC-MS is 200 degrees C for 6 s. Under these conditions, this method gives comparable results to the SDE method.     

Reverse osmosis as a concentration technique for soluble organic phosphorus in fresh water

The chemical nature and availability of soluble organic phosphorus for algal growth is largely unknown. A commercially available reverse osmosis water purification system was adapted for concentrating the soluble organic phosphorus fraction form 100-l volumes of drainage water collected from tile drains underlying an intensively managed grassland area in the Lough Neagh catchment. After membrane filtration the drainage water was recirculated through the reverse osmosis module while the permeate was removed from the system. During a single passage across the reverse osmosis membrane, 20% of the sample was discarded as pure water while the remaining 80% of the sample was pumped back to the reverse osmosis cartridge. Recirculation was continued, with the addition of an intermediate sodium ion-exchange step to prevent the precipitation of insoluble (largely calcium and magnesium) salts, until the volume was reduced to 2.5 l. The recovery of soluble organic phosphorus based on the original sample concentration was almost 93%. A further tenfold increase in concentration was achieved without salt precipitation or loss of soluble organic phosphorus by vacuum-assisted rotary evaporation. The mild, efficient concentration process developed a soluble organic phosphorus concentrate suitable for chemical fractionation and algal availability studies.