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.     

Microwave-Assisted Solvent Extraction of Air Particulates for the Determination of PAHs

A method for the determination of polycyclic aromatic hydrocarbons (PAHs) in air particulates using microwave-assisted solvent extraction (MASE) coupled to a microwave extraction system (MES) is proposed. During the period of August to October, 1994, Singapore was enveloped by haze caused by forest fires in Sumatra, Indonesia. Air sampling were carried out during September and October; the determination of ambient air PAH levels in Singapore was undertaken. PAH analysis by GC-MS provided excellent sensitivity, linearity of quantitation, peak identification. This technique was evaluated using certified reference materials (CRMs) HS-4 and HS-6. Good recoveries of PAHs (>73.3%) were obtained for both CRMs. The MASE technique using MES is suitable for the determination of PAH levels in ambient air with no clean-up step required.     

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.     

Modeling rhizofiltration: heavy-metal uptake by plant roots

The discovery of phytoaccumulation potential of plant species has led to its application for remediation of heavy-metal-contaminated soil and wastewater, which is termed as phytoextraction/rhizofiltration. For prediction, analysis, planning and cost-effective design of such systems, mathematical models not only are used as a screening tool but also provide optimal parameters like harvesting time, irrigation schedule, etc. Several laboratory and field scale studies have been carried out in the past, and mathematical expressions have been developed by various researchers for different phenomena like metal adsorption in soil, plant root growth with time, moisture and metal uptake by plant root, moisture movement in unsaturated zone, soil moisture relationship, etc. The complete design of any such phytoremediation program would require the knowledge of behavior of heavy-metal movement in soil, water and plant root system. In this paper, a model for simulating heavy-metal dynamics in soil, water and plant root system is developed and discussed. The governing non-linear partial differential equation is solved numerically by implicit finite difference method using Picard's iterative technique, and the formulation has been illustrated using a characteristic example. The source code is written in MATLAB.     

Methane emissions from natural wetlands

Methane is considered one of the most important greenhouse gases in the atmosphere. Because of the strict anaerobic conditions required by CH₄-generating microorganisms, natural wetland ecosystems are one of the main sources of biogenic CH₄. The total natural wetland area is estimated to be 5.3 to 5.7 × 10¹² m², making up less than 5% of the Earth's land surface. However, natural wetland plays a disproportionately large role in CH₄ emissions. Wetlands are likely the largest natural sources of CH₄ to the atmosphere, accounting for about 20% of the current global annual emission. Out of the total amount of CH₄ emitted, northern wetlands contribute 34%, temperate wetlands 5%, and tropical systems about 60%.Because of the unique characteristics and high productivity, wetland ecosystems are important in the global carbon cycle. Natural wetlands are permanently or temporarily saturated. Strict anaerobic conditions consequently develop, which allows methanogenesis to occur. But the thin oxic layer and the oxic plant rhizophere promote activity of CH₄-oxidizing bacteria or methanotrophs. Thus, both CH₄ formation and consumption in wetland systems are microbiological processes and are controlled by many factors. Eight of the controlling factors, including carbon supply, soil oxidation-reduction status, pH, temperature, vegetation, salinity and sulfate content, soil hydrological conditions and CH₄ oxidation are discussed in this paper.     

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.     

Study of heat exposure in the work environment in Jeddah

The present work was conducted to define the magnitude of the problem of heat exposure in Jeddah and the role of both the climatic and the industrial factors on the total heat load. Indoor heat exposure was studied in an industrial complex of 5 plants for cables' manufacturing. Outdoor heat exposure was studied in shaded and unshaded operations in Jeddah Islamic Port (JIP). The heat exposure parameters, including air temperature (Ta), wet bulb temperature (Tw), and globe temperature (Tg), as well as the wet bulb globe temperature (WBGT) heat stress index, the relative humidity and the air velocity, were assessed at representative locations. Results of the study indicated that:

Preliminary studies of a fast screening method for polycyclic aromatic hydrocarbons in soil by using solvent microextraction-gas chromatography

Solvent microextraction (SME) was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from spiked and real environmental soil samples with different matrices. Soil sample was mixed with 7 mL of acetone and 14 mL of water to allow partitioning of the PAHs from the soil to the liquid phase. A 2 microL octane drop suspended from a microsyringe needle tip was then immersed into the stirred solution-soil mixture for extraction. After an 11 min extraction, the octane drop was withdrawn into the syringe and injected directly into the GC for identification and quantification. The whole analysis procedure took 27 min, with an extraction time of 11 min, and a GC separation time of 16 min. A second extraction could be undertaken whilst the GC is running, hence the GC run time currently limits the sample throughput. In this method, a small amount of organic solvent was used for the extraction process, which produced little waste. The limits of detection for lower molecular weight (< 230) PAHs range from 0.13 to 0.36 mg kg-1, and for higher molecular weight (> 250) PAHs are estimated to be between 0.5 and 1.0 mg kg-1, with RSD values generally under 20%. Due to the small volumes of organic solvent used, the consumable cost per extraction is only US$ 0.12. This is the first report of the application of SME to solid samples, and the first report of the use of SME for the analysis of PAHs.     

Analysis of two-way layout of count data with negative binomial variation

A number of methods has been proposed for dealing with single-factor or factorial experiments when the requirements for performing the normal theory analysis of variance procedure are not satisfied. This paper suggests the use of the likelihood ratio statistic for testing the main effects and the interaction between the factors in two-way layout of count data following negative binomial distributions with a common dispersion parameter. The likelihood ratio statistic for testing the equality of the dispersion parameters of several groups of count data is also derived. The methods is illustrated by an example concerning the study of spatial and temporal variation of bacterial counts.