Air pollution exposure monitoring and estimation. Part VI. Ambient exposure of adults in an industrialised region

This paper presents methodology and results of a dynamic individual air pollution exposure model (DINEX) that calculates the hourly exposure for each adult in a panel study. Each of over 260 participants, through the use of a diary, provided information used in the model to calculate his/her personal, individualised exposure. The participants filled out the diary daily, hour by hour, over two, two month periods. The exposure assessment model coupled the diary information and results of an indoor/outdoor measurement program, with the results of dispersion modelling on an hourly basis for an industrial area in Norway. The estimated air pollution concentrations from the dispersion model, based on continuous meteorological measurements, were calibrated with air pollutant concentrations measured continuously.     

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.     

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.     

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.     

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.     

Modeling of non-point source pollution in a Mediterranean drainage basin

SWAT ver. 2000 was used to predict hydrographs, and sediment, nitrate and total phosphorus loadings from a 1349 km² mountainous/agricultural watershed in Northern Greece. The model was calibrated and verified using continuous meteorological data from eight stations within the drainage area, and runoff, sediment and nutrient concentrations measured at nine stations located within the main tributaries of the watershed, for the time period from May 1st, 1998 to January 31st, 2000. Model validation methodology and resulting input parameters appropriate for Mediterranean drainage basins are presented. Predicted by the model hydrographs, sedimentographs and pollutographs are plotted against observed values and show good agreement. Model performance is evaluated using the root mean square error computation and scattergrams of predicted versus observed data. The validated model is also used to test the effectiveness of three alternative cropping scenarios in reducing nutrient loadings from the agricultural part of the watershed. The study showed that this model, if properly validated, can be used effectively in testing management scenarios in Mediterranean drainage basins.     

Nonstationary, long memory and anti-persistence in several climatological time series data

In this article we examine the stochastic behaviour of several daily datasets describing sun (total irradiance at the top of the atmosphere and sunspot numbers) and various climatological anomaly series by looking at their orders of integration. We use a testing procedure that permits us to consider fractional degrees of integration. The tests are valid under general forms of serial correlation and deterministic trends and do not require estimation of the fractional differencing parameter. Results show that the series are all nonstationary, with increments that might be stationary for those variables affecting sun, and anti-persistent for those affecting air temperatures.