Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air

Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.     

Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in sewage gas by using cryotrapping gas chromatography inductively coupled plasma mass spectrometry

Evidence for the occurrence of Ni(CO)4 in addition to Mo(CO)6 and W(CO)6 in fermentation gases from a municipal sewage treatment plant is presented for the first time. The gases were sampled at the top of the sewage sludge digester using Tedlar bags, and were analysed using cryotrapping followed by gas chromatography coupled with inductively coupled mass spectrometry (GC-ICP-MS). The use of an ICP-MS as an element-specific detector gives sufficiently low detection limits for metals and was coupled to a packed column gas chromatograph. This method provides information about the speciation of volatile transition metals in contrast to previously used methods for the determination of Ni(CO)4 in gas samples. The element-specific detection of three different isotopes (m/z 58, 60, 62) and the correspondence of the samples' retention times with those of the standard provided convincing evidence that Ni(CO)4 is present in the fermentation gas. The concentrations found were in the sub-ppb level, which is at least one order of magnitude lower than the threshold level of 1 ppb (v/v). In addition, Mo(CO)6 and W(CO)6 were also measured in the sub-ppb range in contrast to the absence of Fe(CO)5. The stabilities of Ni(CO)4, Fe(CO)5, and Mo(CO)6 were tested in a carbon monoxide atmosphere. In the presence of distilled water, the following order of stability was found after 11 weeks: Fe(CO)5 < Ni(CO)4 < Mo(CO)6. In the presence of an aqueous solution containing nickel, molybdenum, tungsten and iron, however, only Fe(CO)5 was significantly decomposed (< 0.3% recovery); Ni(CO)4 and Mo(CO)6 were stable after 11 weeks. No W(CO)6 was formed. The low stability of Fe(CO)5 in the presence of water could be the reason why no volatile iron compound was found in sewage gas. This study showed that GC-ICP-MS can be employed to identify species-specific traces of metal carbonyls in process gases such as sewage gas.     

Soil Lead and Other Metal Levels in Industrial, Residential and Nature Reserve Areas in Singapore

The use of pressure feedback microwave digestion technique has permitted rapid and efficient digestion of soil and sediment samples. The evaluation of different acid mixtures to digest soil samples were studied by mixed-level orthogonal array design. The selected acid mixture of HCl-HNO3-HF was employed in the survey of Pb, Zn, Cu, Cr and Mn in soil samples. Surface soil samples were collected from industrial, residential and nature reserve areas in Singapore. The five metal concentrations were determined by flame atomic absorption spectrometry and graphite furnace atomic absorption spectrometry. The lead and other metal contents in NBS SRM 1645, NIES CRM No. 2 and NRCC BCSS-1 sediment standard references were determined concurrently with the survey samples. Five measured metal loading on the surface soils was in the order: industrial area > residential area > nature reserve area. The trace metal concentrations in surface soil from areas of heavy traffic are higher than those from residential areas. The main sources of trace metal pollution are vehicular exhaust and industrial activities.     

Study of Meteorological Aspects and Urban Concentration of SO2 in Atmospheric Environment of La Plata, Argentina

This article presents and discusses SO₂ (ppbv) concentration measurements combined with meteorological data (mainly wind speed and direction) for a five-year campaign (1996 to 2000), in a site near an oil refinery plant close to the city of La Plata and surroundings (aprox. 740.000 inh.), considered one of the six most affected cities by air pollution in the country. Since there is no monitoring network in the area, the obtained results should be considered as medium term accumulated data that enables to determine trends by analyzing together gas concentrations and meteorological parameters. Preliminary characterization of the behaviour of the predominant winds of the region in relation with potential atmospheric gas pollutants from seasonal wind roses is possible to carry out from the data. These results are complemented with monthly averaged SO₂ measurements. In particular, for year 2000, pollutant roses were determined which enable predictions about contamination emission sources. As a general result we can state that there is a clear increase in annual SO₂ concentration and that the selected site should be considered as a key site for future survey monitoring network deployment. Annual SO₂ average concentration and prevailing seasonal winds determined in this work, together with the potential health impact of SO₂ reveals the need for a comprehensive and systematic study involving particulate matter an other basic pollutant gases.     

博斯腾湖水质矿化度模型及预测研究

根据博斯腾湖１９８５～１９９５年水质监测数据和出入湖水量等水文数据观测值，采用水质扩散模型和盐量平衡关系推导出博斯腾湖大湖区（简称博湖）水质矿化度模型，并预测了几种情况下博湖水质矿化度及近几年变化趋势，分析了影响博湖水质矿化度的主要因素，为博湖的近期和远期环境保护规划、环境管理等提供科学依据．     

地下水环境质量变化动态研究

以邢台市环境保护监测站１０年来的监测资料为依据，运用单因子比值法，环比发展速率外推法和直线回归法，对地下水环境质量现状及１０年的动态变化进行了分析，研究和评述，并对发展趋势做了预测性评价。     

Trends in motor-vehicle related air pollutants in central London

Results of intermittent monitoring of six aromatic hydrocarbons (benzene, toluene, ethyl-benzene, m-xylene, p-xylene and o-xylene), carbon monoxide and oxides of nitrogen over a thirteen year period at a site in central London (Exhibition Road) are presented. Four monitoring regimes were undertaken; namely, 1979, 1982/83, 1986/87 and 1991/92. The summertime daytime mean ambient concentrations of the measured parameters at this site are presented. The reported concentrations show a reduction from 1979 to 1992 by approximately a factor of two, despite national increases in motor fuel consumption and the volume of traffic. Relevant European Community legislation covering emissions from motor-vehicles are outlined and comparisons are made with emissions from motor vehicles predicted from the UK national inventory. The importance of the frequency of measurements was also noted.     

Overstory mortality as an indicator of forest health in California

The interagency Forest Health Monitoring Program involves a network of about 4200 forest plots on a triangular grid across the United States. We present data on recent mortality of trees 27.9 cm diameter from the first three years of measurements in California (1992–1994). Three plot designs were used to collect data representative of a 1-ha stand at each site; the designs differed primarily in total area sampled (0.067, 0.4 and 1.0 ha). Approximately 50 sites were visited each year yielding a total of about 150. Field tallies showed few cases of recent mortality in the smallest plot size. Cumulative distribution functions of recent dead tree densities in the 0.067-ha plots differed significantly from those generated by tallies from entire 1-ha stands. We conclude that an area of 0.067 ha is unsuitable to assess and monitor overstory mortality in Pacific Coast forests.The U.S. government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

A ten channel fibre-optic device for distributed sensing of underground hydrocarbon leakage

With millions of fuel storage tanks and oil pipelines installed around the world, there is inevitably frequent leakage of potentially hazardous hydrocarbons. As many of these installations are below ground, it can often be many years before the extent of the leak is discovered. We have previously reported the development of a sensor for the detection of such subterranean leaks, using infrared reflectometry to interrogate a hydrocarbon sensitive membrane. However, a single sensor cannot provide any information about the flow rate or direction of the leak. This paper describes the extension of the technology to a multi-channel distributed sensing system, using optical fibres capable of distributing the sensors over large subterranean areas. Results are reported from the evaluation of the device, which consisted of monitoring the movement of different hydrocarbons (gasoline, diesel and insulating oil) through a vertical sand-filled vessel.