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.     

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.     

evaluation of a measurement method for forest vegetation in a large-scale ecological survey

We evaluate a field method for determining species richness andcanopy cover of vascular plants for the Forest Health MonitoringProgram (FHM), an ecological survey of U.S. forests. Measurementsare taken within 12 1-m² quadrats on 1/15 ha plots in FHM.Species richness and cover are determined for four height classes(strata) within each quadrat and aggregated by stratum over the entireplot. We estimated (1) the agreement between experienced trainers andinexperienced technicians who collected the data on this survey(accuracy) and (2) the agreement among the technicians (precision) forresults on species richness and cover from 3 test plots at 3 timeintervals. The methods appear to be highly precise, although somediscrepancies with the values obtained by the trainers were found.Trainers found significantly more species in the ground stratum (0–0.6 m) and measured significantly more cover in the uppermost stratum(>4.9 m). The proportion of variation due to measurement error andtemporal variability was less than 13% for species richness (all strata)and cover (all but one stratum). This indicates that the method issuitable for monitoring changes in species richness and canopy coverfor a large-scale synoptic monitoring project such as FHM.     

Chemical and Bacteriological Monitoring of Drinking Water from an Urbanised Water Catchment Drainage Basin

The Linggi river drainage basin in Negeri Sembilan, Malaysia supplies water to the whole of Port Dickson district and meets 50% of the Seremban district needs. The Linggi River, the main tributary, passes through the highly urbanised and densely populated Seremban district while the water treatment plant is located 16 km downstream. In 1979 the USEPA declared the river unsuitable as a source of raw water whereas the WHO classified it as being heavily polluted requiring more extensive and effective treatment. In order to meet the WHO drinking water standards, an ozonation system was installed in the conventional water treatment plant. The objective of ozonation is for the control and removal of organic micropollutants and other deleterious matters. This study investigated the concentrations and distribution of organic micropollutants, heavy metals, and bacteriological counts in water samples collected from within the catchment and the treated water. The effectiveness of the ozonation system was also studied. The total level of phenolic water pollutants in the catchment was generally found to be very much higher than the maximum recommended level of 2.0 µgl-1. The extensive treatment process carried out at the plant was very effective in reducing the levels of total phenols in the treated water to less than 1.0 µgl-1. However the process was not efficient enough to reduce the levels of some heavy metals as required by the standards, for examples Cd and Pb were still three times higher than the standards of 5µgl-1 and 0.05 mgl-1 respectively. For bacteriological study, coliform group of bacteria, Salmonella, faecal streptococci and injured coliform were monitored in the raw and treated water. The raw water contained coliforms about 1000 times higher than the required standard for raw ater, but after the secondary treatment by ozonation coliform bacteria were absent, however a small number of Salmonella was still present occasionally. The study also showed that restructuring of the district and relocating of some commercial activities along the river banks to other areas carried out over the last five years has improved the general quality of the river water.     

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.     

A Global Overview of Atmospheric Acid Deposition Fluxes

This paper presents a summary of globalacid deposition flux data taken from a globalassessment report on acid deposition prepared forUNEP/WMO (Whelpdale and Kaiser, 1996). There is a largevariation in the spacial coverage and reliability ofmonitoring around the world. Many more stationsmeasure wet deposition than collect appropriate datafor estimating dry deposition. The widespread regionswith highest precipitation concentrations anddeposition fluxes of sulphate and nitrate coincideclosely with the regions of highest density ofSO₂ and NO_x precursor emissions occurringprimarily in the mid-latitude, northern hemispherebelt where a large fraction of the worlds fossilfuels is consumed. Organic acids in precipitation makea minor contribution to acidity (<20%) inindustrial regions, but in the rest of the world theyare of same order, or even exceed, inorganic acids.Less is known about dry deposition, but it appears topredominate near strong emission sources with wetdeposition predominating farther downwind. The molarratio of the N/S contribution to acidic deposition isclose to 1.0 over large areas of Europe and NorthAmerica, but is highly variable elsewhere, beinghighest in equatorial regions due to biomass burningand lowest near smelters and other large sources of SO₂.     

RISK ASSESSMENT METHODOLOGY FOR KARST AQUIFERS: (2) SOLUTE-TRANSPORT MODELING

Ground-water flow and solute-transport simulation modeling are major components of most exposure and risk assessments of contaminated aquifers. Model simulations provide information on the spatial and temporal distributions of contaminants in subsurface media but are difficult to apply to karst aquifers in which conduit flow is important. Ground-water flow and solute transport in karst conduits typically display rapid-flow velocities, turbulent-flow regimes, concentrated pollutant-mass discharge, and exhibit open-channel or closed-conduit flow. Conventional ground-water models, dependent on the applicability of Darcy`s law, are inappropriate when applied to karst aquifers because of the (1) nonapplicability of Darcian-flow parameters, (2) typically nonlaminar flow regime, and (3) inability to locate the karst conduits through which most flow and contaminant transport occurs. Surface-water flow and solute-transport models conditioned on a set of parameters determined empirically from quantitative ground-water tracing studies may be effectively used to render fate-and-transport values of contaminants in karst conduits. Hydraulic-flow and geometric parameters developed in a companion paper were used in the surface-water model, TOXI5, to simulate hypothetical slug and continuous-source releases of ethylbenzene in a karst conduit. TOXI5 simulation results showed considerable improvement for predicted ethylbenzene-transport rates and concentrations over qualitative tracing and analytical ground-water model results. Ethylbenzene concentrations predicted by TOXI5 simulations were evaluated in exposure and risk assessment models.     

Optimal charges on river effluent from lumped and distributed sources

We propose a modelling framework for the design of a Pigouvian effluent tax, in an environmental management problem implicating several economic agents located in a river basin. The proposed charging system allows for the agents' geographical position relative to the river's sections, at which environmental standards are to be enforced, and takes into account the possible different market structures within which the agents are operating. In particular, we consider industrial agents competing on an oligopolistic market, and a set of farmers acting as price takers on a large market. A regional authority's goal is to induce agents to some sort of cooperation which would result in the satisfaction of the common environmental constraints. The economic process on one side, and the pollution transport and accumulation on the other, constitute two dynamic processes in two different time scales. As the economic process is much slower than the other process we can neglect the latter's transients and concentrate on the time invariant steady state solutions to the transportation equation. The model thus constructed has some noncooperative game and optimal control problem's features with space being the ‘running’ variable. This revised version was published online in July 2006 with corrections to the Cover Date.