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.     

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.     

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.     

Hydropower production and river rehabilitation: A case study on an alpine river

Despite the numerous benefits of hydropower production, this renewable energy source can have serious negative consequences on the environment. For example, dams act as barriers for the longitudinal migration of organisms and transport of particulate matter. Accelerated siltation processes in the receiving river reduce the vertical connectivity between river and groundwater. Hydropeaks, caused by short-term changes in hydropower operation, result in a negative impact on both habitat and organisms, especially during winter months when natural discharge is low and almost constant. In this study, we report the current deficits present in the River Rhone from two different scientific perspectives – fish ecology and hydrology. Potential rehabilitation solutions in synergy with flood protection measures are discussed. We focus on the effects of hydropeaking in relation to longitudinal and vertical dimensions and discuss local river widening as a potential rehabilitation tool. The fish fauna in the Rhone is characterized by a highly unnatural structure (low diversity, impaired age distribution). A high correlation between fish biomass and monotonous morphology (poor cover availability) was established. Tracer hydrology provided further details about the reduced permeability of the riverbank, revealing a high degree of siltation with K values of about 4.7 × 10^?6 m s^?1. Improving the hydrologic situation is therefore essential for the successful rehabilitation of the Rhone River. To this end, hydropeaks in the river reaches must be attenuated. This can be realized by a combination of different hard technical and soft operational measures such as retention reservoirs or slower up and down ramping of turbines.     

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.     

Estimating Trophic State Proportions of a Regional Lake Population: Are Larger Samples Always Better?

During the summers of 1991–1994, the Environmental Monitoringand Assessment Program (EMAP) sampled 344 lakes throughout thenortheastern United States using a proportional stratified sampling design based on lake size. Approximately one-quarter ofthe 344 lakes were sampled each year (4 years) for totalphosphorus to determine the proportion (and associated95% confidence intervals) of the northeast lake population 1ha (11,076 ± 1,699 lakes) that was in oligotrophic,mesotrophic, eutrophic, or heupereutropic (4 classes) conditionaccording to the total phosphorus criteria of the North AmericaLake Manegement Society. Estimates for the second, third, andfourth yr were developed as cumulative of the previous yrsamples and the current yr samples for the northeast as a wholeand for each of its three ecoregions (4 regions). New confidence intervals were computed for each cumulative yrcondition estimate. This produced a total (4 years × 4classes × 4 regions) of 64 cumulative yr tropic conditionestimates. Confidence intervals for 21% of these estimates didnot shorten with increased sample size. This phenomena raisedquestions about the accuracy of estimates based on cumulativesampling procedures. We explain why and how the phenomenon comesabout with both straight random and proportional randomsampling. Further, we present an example of the effects thisphenomenon has on lake tropic state condition estimates in thenortheastern United States.     

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.