Tritium in a Pine Forest Ecosystem: Relation between Fresh Pine Needles, Organic Materials on a Forest Floor and Atmosphere

Tritium concentrations were analyzed in organic and water fractions of fresh pine needles, dead and degraded pine needles accumulating on a pine forest floor to examine tritium cycle in a forest ecosystem. Tritium concentration was higher in the organic fraction of dead and degraded pine needles compared to others, suggesting two tritium sources. Rain is responsible for water fractions in the samples, while atmospheric hydrogen and methane are speculated to be responsible for high tritium level in the organic fraction of dead and degraded pine needles.     

Open wet ashing of some types of biological materials for the determination of mercury and other toxic elements

An open wet decomposition procedure for trace element analysis of biological material has been worked out. It is based on the utilization of nitric acid, hydrochloric acid and hydrogen peroxide and is well suited for the determination of As, Bi, Cd, Cr, Hg, Pb, Sb, Se and Tl. For these elements the recoveries were examined by the radiotracer technique, with lichens, pine needles, grass and human hair as representative biological samples. In addition to the conventional labelling technique, use was also made of in situ labelling. In all cases, recoveries between 93 and 100% were achieved, which are adequate for quantitative trace element analysis.     

Response of air-pollution biomonitors under three different meteorological conditions

Samples of Flavoparmelia caperata (L.) Hale thalli, from a clean area in northern Portugal (Baião), were transplanted into exposure locations at the western Atlantic coast (north, center and south) impacted by urban-industrial emissions and meteorologically different, for a ten-month long experiment split into five terms of assessment (two months each). Through the experiment, the sites were also monitored for atmospheric bulk deposition. Analytical techniques for determinations in lichens and bulk deposition were instrumental neutron activation analysis, atomic absorption spectrophotometry and inductively coupled plasma mass spectrometry. The results indicate that: (1) the biological signals of detached lichens are compatible with sources in the area; (2) there is an appreciable number of airborne elements significantly enriched in (exposed) lichen samples, including some of great environmental interest; and (3) the cumulative contents per unit area of detached-lichen material are likely to provide an acceptable estimate of the atmospheric availability of enriched elements, as measured by their cumulative contents in the dry residues of bulk deposition.     

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.     

Acid digestion of geological and environmental samples using open-vessel focused microwave digestion

The application of open vessel focused microwave acid digestion is described for the preparation of geological and environmental samples for analysis using inductively coupled plasma-mass spectrometry (ICP-MS). The method is compared to conventional closed-vessel high pressure methods which are limited in the use of HF to break down silicates. Open-vessel acid digestion more conveniently enables the use of HF to remove Si from geological and plant samples as volatile SiF4, as well as evaporation-to-dryness and sequential acid addition during the procedure. Rock reference materials (G-2 granite, MRG-1 gabbros, SY-2 syenite, JA-1 andesite, and JB-2 and SRM-688 basalts) and plant reference materials (BCR and IAEA lichens, peach leaves, apple leaves, Durham wheat flour, and pine needles) were digested with results comparable to conventional hotplate digestion. The microwave digestion method gave poor results for granitic samples containing refractory minerals, however fusion was the preferred method of preparation for these samples. Sample preparation time was reduced from several days, using conventional hotplate digestion method, to one hour per sample using our microwave method.     

Intercomparison of moss reference material by different multi-element techniques

An intercomparison of data obtained for a moss reference material (Hylocomium splendens) used as biomonitor of atmospheric deposition by different multi-element techniques is presented. In total 43 elements (Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Ag, Sn, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, Ta, W, Au, Th, U) were determined using inductively coupled plasma-mass spectrometry (ICP-MS), conventional instrumental neutron activation analysis (INAA), epithermal neutron activation analysis (ENAA) and as well as shorttime neutron activation analysis without and with a⁶LiD-converter. Advantages and drawbacks of each method are discussed. The introduction of moss reference materials for atmospheric multi-element deposition studies involving nuclear analytical techniques is strongly recommended.     

Concentration and vertical distribution of plutonium and americium in Italian mosses and lichens

The plutonium and americium concentration and vertical distribution in some Italian mosses and lichens have been determined. The^239,240Pu,²³⁸Pu and²⁴¹Am concentration ranges in tree trunk lichens 0.83–1.87, 0.052–0.154 and 0.180–0.770 Bq/kg, respectively. The corresponding values in tree mosses are higher and more scattered ranging from 0.321 to 4.96, from 0.029 to 0.171 and from 0.200 to 1.93 Bq/kg. The mean²³⁸Pu/^239,240Pu and²⁴¹Am/^239,240Pu ratios are 0.088±0.037 and 0.38±0.13 in lichens and 0.091±0.072 and 0.54±0.16 in tree mosses. The Pu and Am concentrations are relatively low in terrestrial mosses. The^239,240Pu,²³⁸Pu and²⁴¹Am vertical distributions in a terrestrial moss core (Neckera Crispa) collected near Urbino (central Italy) show an exponential decrease with the height. On the contrary the²⁴¹Am vertical distribution in another terrestrial moss core (Sphagnum Compactum) collected in the Alps (northern Italy) shows an interesting peak at 16 cm which corresponds to the deposition of fallout from the nuclear weapon tests in 1960's. The²⁴¹Am movement upward and downward in the moss core is also studied. The results show once again that both mosses and lichens are very effective accumulators of Pu and Am and that they can be used as good biological indicators of the radionuclide airbome pollution from nuclear facilities and nuclear weapon tests. They can play a very impotant role in cycling naturally or artificially enhanced radionuclides in the atmosphere over long time scales.     

电感耦合等离子体质谱(ICP-MS)法结合化学计量学分析比较6种松针中无机元素的含量

为研究甘肃地区松针中无机元素的含量,探究不同品种松针中无机元素的差异,采用HNO₃(65%)对松针样品进行微波消解,电感耦合等离子体质谱(ICP-MS)法测定甘肃两地区6种松针中28种无机元素的含量,结合主成分分析以及偏最小二乘判别分析对松针地区差异进行判别;结果显示松针中无机元素含量丰富,其中Na、Mg、Al、K、Ca、Fe、Zn、Mn、Sr等元素在不同品种松针中均有较高含量,主成分分析结果显示共有7个主成分,累积贡献率达到92.58%,偏最小二乘判别分析显示两地区6种松针在地区上可被明显分开,其中Mg、Fe、Zn、Mn、Sr、K 6种元素为造成地区差异的主要元素。实验结果表明松针中元素种类丰富,人体必需微量元素含量较高,且不同地区松针在地区上具有一定的一致性和特异性。     

Comparison of metal concentrations in three species of mosses and metal freights in bulk precipitations

Concentration of 25 trace metals in mosses ( Hylocomium splendens, Pleurozium schreberi and Hypnum cupressiforme) are compared with bulk deposition freights (Bergerhoff method) at 3 sites in Switzerland, one on the plateau, a second in the northern prealps and a third in the southern alps. The three moss species are interchangeable and the atmospheric background deposition can be estimated with sufficient accuracy for Ag, Al, As, Cd, Ce, Co, Cr, Cu, Fe, Ga, Ge, La, Li, Mo, Nb, Ni, Pb, Th, Ti, U, V, W, Y, Zn. For Hg this study does not give definite results. No seasonal differences in moss concentrations from spring to autumn can be shown.     

Atmospheric deposition of heavy metals in northern Serbia and Bosnia-Herzegovina studied by the moss biomonitoring, neutron activation analysis and GIS technology

The results on atmospheric deposition of heavy metals and other trace elements using the moss biomonitoring technique in the northern part of Serbia and some areas of Bosnia-Herzegovina are presented. Samples of Hypnum cupressiforme along with some other moss types were collected at 92 sites during the summer of 2000. A total of 44 elements were determined by INAA using epithermal neutrons. High values of Cl and V content in the moss samples at certain areas are suspected to be associated with fires in oil refineries damaged during the 1999 NATO military action.     

Pine Needles (Pinus Sylvestris) as a Bioindicator of Sulphur and Heavy Metal Deposition in the Area Around a Pulp and Paper Mill Complex at Kemi,Northern Finland

Abstract

The determination of sulphur and heavy metals in plants is an integral part of many environmental studies. Pine needles (Pinus Sylvestris) have proved to be suitable air quality indicators for pollutants, especially for sulphur. This study was carried out in the vicinity of Kemi, a town situated on the Gulf of Bothnia in northern Finland. An industrial complex comprising two pulp and paper mills is located in the centre of the area. Scots pine (Pinus Sylvestris) needles were collected from 29 sampling sites. The samples were dried, homogenized and digested with nitric acid. The concentrations of the elements S, Fe, Zn, Ca, V, and Pb were determined by ICP-AES. According to our results pine needles (Pinus sylvestris) appear to be an ideal bioindicator and sampling material for identifying and assessing atmospheric sulphur pollution derived from pulp and paper mills and can complement the information provided by plant mapping studies around pulp and paper mills.     

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%.     

Comparison of metal concentrations in three species of mosses and metal freights in bulk precipitations

Concentration of 25 trace metals in mosses (Hylocomium splendens, Pleurozium schreberi and Hypnum cupressiforme) are compared with bulk deposition freights (Bergerhoff method) at 3 sites in Switzerland, one on the plateau, a second in the northern prealps and a third in the southern alps. The three moss species are interchangeable and the atmospheric background deposition can be estimated with sufficient accuracy for Ag, Al, As, Cd, Ce, Co, Cr, Cu, Fe, Ga, Ge, La, Li, Mo, Nb, Ni, Pb, Th, Ti, U, V, W, Y, Zn. For Hg this study does not give definite results. No seasonal differences in moss concentrations from spring to autumn can be shown.     

Measurement of L shell X-ray fluorescence intensity ratios for some elements in the atomic number range of 66£Z£90 by photoionization of consecutive L-subshells

In 1999 investigation, the needles of Sabina chinesis L. from 11 hot spot tourist cities extending over China were collected as biomonitors for evaluation of atmospheric elemental differences in those cities. Thirty five elements were determined by instrumental neutron activation analysis (INAA). The experimental data reflected the environmental alteration in the cities that have different geographical position, population burden and industrialized level. Eventually by using the data processed by factor analysis (FA) and subsequent cluster analysis (CA), the cities were grouped into six sorts of the urban atmospheric deposition with corresponding elements.     

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.     

Determination of twenty-five elements in lichens by sector field inductively coupled plasma mass spectrometry and microwave-assisted acid digestion

A simple and efficient digestion method for rapid sample preparation and quantification of 25 chemical elements in lichens by sector field inductively coupled plasma mass spectrometry is described. A microwave (MW)-assisted acid digestion was carried out at atmospheric pressure simultaneously handling up to 80 samples in screw-capped disposable polystyrene tubes. This digestion procedure was compared with the established MW digestion in closed vessels in order to examine its potential applicability in routine analysis for environmental monitoring. Three certified reference materials, i.e. BCR 482 (lichens), BCR 62 (olive leaves) and BCR 100 (beech leaves), as well as a small set of real samples were analyzed. Limits of quantification, accuracy and precision of the method were assessed. The majority of the elements were totally recovered from the lichens and from the other vegetable matrices. Low contamination risk, simplicity, time-saving, and applicability in routine analyses make this method very suitable for use in extensive screening campaigns.     

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.     

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。     

Moss as monitor of heavy metal deposition: Comparison of different multi-element analytical techniques

Instrumental activation analysis (INAA) based on irradiations in a nuclear reactor with particularly high relative fluxes of resonance and fast neutrons has been shown to open new possibilities for multi-element surveys of mosses used as monitors of atmospheric deposition. Comparison is made with data obtained by inductively coupled plasma-mass spectrometry (ICP-MS) and conventional INAA. Data for 15 elements not previously investigated in routine moss studies are presented, e.g., Zr, Sn, Hf, Ta, W, Au, Th, and the rare earth elements Ce, Nd, Eu, Gd, Tb, Tm, Yb, Lu. Other elements particularly well determined by this approach are Sc, Co, As, Ag, Sb, Cs, La, Sm, Th, and the non-metallic trace elements Se, Br, and I. Advantages and drawbacks with the high fast neutron component are discussed.     

Reference materials for large-scale metal deposition surveys

 In order to ensure quality assurance in large-scale environmental contamination studies involving many different analytical laboratories, the use of calibrated reference materials is essential. Prior to a survey of atmospheric metal deposition in 1995 comprising 20 countries and covering large parts of Europe, the lack of suitable reference materials of moss and organic-rich soil was apparent. In order to improve the quality of analytical data to be produced in this international survey, candidate analytical laboratories were invited to participate in an intercomparison exercise. Three moss and three soil humus reference samples specifically prepared for this purpose were distributed anonymously among the laboratories, which were asked to report data for ten priority elements (V, Cr, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb) and as many additional elements as they determined normally. In this paper the analytical data from the intercomparison are evaluated, and recommended values for the ten priority elements and 17 additional elements (B, Na, Mg, Al, S, K, Ca, Mn, Co, Se, Rb, Sr, Sb, Cs, Ba, La, Th) in each of the six reference samples are established. These samples should be useful for similar future studies including areas where the contamination levels are very low. Received: 17 October 1996 Accepted: 2 January 1997