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.     

The extraction of aged polycyclic aromatic hydrocarbon (PAH) residues from a clay soil using sonication and a Soxhlet procedure: a comparative study

A sonication method was compared with Soxhlet extraction for recovering polycyclic aromatic hydrocarbons (PAH) from a clay soil that had been contaminated with tar materials for several decades. Using sonication over an 8 h extraction period, maximum extraction of the 16 US EPA priority PAH was obtained with dichloromethane (DCM)-acetone (1 + 1). The same procedure using hexane-acetone (1 + 1) recovered 86% of that obtained using DCM-acetone (1 + 1). PAH recovery was dependent on time of extraction up to a period of 8 h. The sonication procedure showed that individual PAH are extracted at differing rates depending on the number of fused rings in the molecule. Soxhlet extraction [with DCM-acetone (1 + 1)] over an 8 h period recovered 95% of the PAH removed by the sonication procedure using DCM-acetone (1 + 1), indicating that rigorous sonication can achieve PAH recoveries similar to those obtained by Soxhlet extraction. The lower recovery with the Soxhlet extraction was explained by the observed losses of the volatile PAH components after 1-4 h of extraction. The type of solvent used, the length of time of extraction and extraction method influenced the quantification of PAH in the soil. Therefore, the study has implications for PAH analyses in soils and sediments, and particularly for contaminated site assessments where the data from commercial laboratories are being used. The study emphasizes the importance of establishing (and being consistent in the application of) a vigorous extraction, particularly for commercial laboratories that handle samples of soil in batches (at different times) from a single site investigation or remediation process. The strong binding of PAH to soil, forming aged residues, has significant implications for extraction efficiency. This paper illustrates the problem of the underestimation of PAH using the US EPA method 3550, specifically where a surrogate spike is routinely employed and the efficiency of the extraction procedure for aged residues is unknown. The implications of this study for environmental monitoring, particularly where numerous batches of samples from a single site assessment or remediation program are submitted to commercial laboratories, is that it would be advisable for these laboratories to check their existing method's extraction efficiencies by conducting a time course sonication extraction on their particular soil to determine the optimum extraction time.     

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.     

Study of the relationships between bone lead levels and its variation with time and the cumulative blood lead index, in a repeated bone lead survey

The study aims were to: (i) investigate long term human lead metabolism by measuring the change of lead concentration in the tibia and calcaneus; and (ii) assess whether improved industrial hygiene was resulting in a slow accumulation of lead in an exposed workforce. 109Cd excited K X-ray fluorescence was used to measure tibia lead and calcaneus lead concentrations in 101 workers in a secondary lead smelter. 51 subjects had had similar bone lead measurements 5 years previously. Most of the other subjects had been hired since the first survey. Measurements of whole blood lead were available for the large majority of subjects. Tibia lead concentrations fell significantly (p<0.001) in the 51 subjects with repeated bone lead measurements, from a mean of 39 microg Pb (g bone mineral)(-1) to 33 microg Pb (g bone mineral)(-1). The change correlated negatively with the initial tibia lead concentration, producing an estimate for an overall half-life of 15 years, with a 95% confidence interval of 9 to 55 years. Adding continuing lead exposure and recirculation of bone lead stores to the regression models produced half-life estimates of 12 and 9 years, respectively, for release of lead from the tibia. The repeat subjects showed no net change in calcaneus lead (64 microg Pb (g bone mineral)(-1) initially, 65 microg Pb (g bone mineral)(-1) 5 years later). Subjects not measured previously had average lead concentrations of 15 microg Pb (g bone mincral)(-1) in the tibia and 13 microg Pb (g bone mineral)(-1) in the calcaneus. The rate of clearance of lead from the tibia (9 to 15 years) is towards the more rapid end of previous estimates. The lack of a significant fall in the calcaneus lead was surprising. Attempts should be made to repeat this observation. If confirmed, it would have implications for models of lead metabolism. The relatively low lead concentrations in the non-repeat subjects are reassuring. However, observation after a longer period of employment would be desirable.     

Exploring data quality for some inorganic and organic constituents of inhalable particulate matter (PM10)

Quality assurance (QA) assessments of air pollution data sets provide a basis for evaluating the significance of various substances in the atmosphere. For non-criteria pollutants, QA results are seldom reported in the technical literature and are often difficult to estimate. The present report provides a summary of QA results such as recovery, precision and accuracy data. Of the six trace elements and nine organic constituents compared in detail, recoveries, laboratory precision and laboratory accuracy values were 100%, ±3% to ±19% and-2 to-13% for the former group and 69% to 98%, ±7% to 23% and-15 to-34% for the later group. System precision varied from ±22% to ±47% for the trace elements and ±42% to ±83% for the organic constituents. Limitations in the interpretation of non-criteria particulate-phase pollutant data bases are discussed with some emphasis placed on receptor-modelling and risk assessment applications. Finally, the relevance of NBS certified materials for QA estimates in non-criteria air pollutant studies is also reviewed.     

Environmental audits: Proposed terminology

This paper presents a review of the fast developing subject of environmental auditing with the authors proposing a series of definitions. Of particular concern is a move towards the development of an accepted vocabulary for environmental impact assessment, even though the international dimension of the subject makes this a difficult task. Use of the word audit has become an accepted part of EIA vocabulary, however there are several types of audits being undertaken today. Presently, there are no commonly accepted definitions, consequently this paper will attempts to address this issue. Definitions for seven types of environmental audits are suggested, derived from the experience of the authors and from a review of the current literature. It is hoped that by the presentation of these definitions that such terms will be advocated for future EIA work, and thereby reducing confusion that otherwise may occur. The paper concludes with a brief review of the status of auditing.