Development and evaluation of a continuous coarse (PM10-PM2.5) particle monitor

In this paper, we describe the development and laboratory and field evaluation of a continuous coarse (2.5-10 microm) particle mass (PM) monitor that can provide reliable measurements of the coarse mass (CM) concentrations in time intervals as short as 5-10 min. The operating principle of the monitor is based on enriching CM concentrations by a factor of approximately 25 by means of a 2.5-microm cut point round nozzle virtual impactor while maintaining fine mass (FM)--that is, the mass of PM2.5 at ambient concentrations. The aerosol mixture is subsequently drawn through a standard tapered element oscillating microbalance (TEOM), the response of which is dominated by the contributions of the CM, due to concentration enrichment. Findings from the field study ascertain that a TEOM coupled with a PM10 inlet followed by a 2.5-microm cut point round nozzle virtual impactor can be used successfully for continuous CM concentration measurements. The average concentration-enriched CM concentrations measured by the TEOM were 26-27 times higher than those measured by the time-integrated PM10 samplers [the micro-orifice uniform deposit impactor (MOUDI) and the Partisol] and were highly correlated. CM concentrations measured by the concentration-enriched TEOM were independent of the ambient FM-to-CM concentration ratio, due to the decrease in ambient coarse particle mass median diameter with an increasing FM-to-CM concentration ratio. Finally, our results illustrate one of the main problems associated with the use of real impactors to sample particles at relative humidity (RH) values less than 40%. While PM10 concentrations obtained by means of the MOUDI and Partisol were in excellent agreement, CM concentrations measured by the MOUDI were low by 20%, and FM concentrations were high by a factor of 5, together suggesting particle bounce at low RH.     

The use of sediment analogues to study the uptake of pollutants by chironomid larvae

A technique is described that uses artificial resin beads with known surface properties to investigate the factors influencing the bioaccumulation of pollutants from sediments. One advantage of this technique is that it provides a standard procedure against which it is possible to calibrate natural sediments with their diverse properties. The method has been used on third instar larvae of the midge Chironomus riparius and the results are compared with previous studies on the worm Lumbriculus variegatus. The use of a standard test using resin beads as a substitute for natural sediment allows comparisons to be made between species and substrates. Thus, the bioaccumulation factors for the midge larvae are much smaller than those of the worm and this correlates with the ability of the insect larva to detoxify many pollutants. It is also possible to use the test to identify if ingestion of the sediment increases the bioaccumulation of contaminants and whether this involves the release of pollutants by digestive processes or not.     

One-dimensional simulation of solute transfer in saturated-unsaturated porous media using the discontinuous finite elements method

A one-dimensional transport model for simulating water flow and solute transport in homogeneous-heterogeneous, saturated-unsaturated porous media is presented. The model is composed of a combination of accurate numerical algorithms for solving the nonlinear Richard's and advection-dispersion equations (ADE). The mixed form of Richard's equation is solved using a standard finite element method (FEM) with primary variable switching. The transport equation is solved using operator splitting, with the discontinuous finite element method (DFE) for discretization of the advective term. A slope limiting procedure for DFE avoids numerical instabilities but creates very limited numerical dispersion for high Peclet numbers. An implicit finite differences scheme (FD) is used for the dispersive term. The unsaturated flow and transport model (Wamos-T) is applied to a variety of rigorous problems including transient flow, heterogeneous medium and abrupt variations of velocity in magnitude and direction due to time-varying boundary conditions. It produces accurate and mass-conservative solutions for a very large range of grid Peclet numbers. The Wamos-T model is a good and robust alternative for the simulation of mass transport in unsaturated domain.     

On the hydro-dispersive equivalence between multi-layered mineral barriers

In the context of municipal solid waste and hazardous waste disposal, the notion of "equivalence" between different barrier designs appears in regulatory documents from several industrialized countries. While in the past, equivalence has been thought of mainly in terms of contaminant travel times, in recent years it has been defined more in terms of the magnitude of a disposal site's potential impact on groundwater resources. This paper presents some original analytical solutions to the problem of contaminant migration through a multi-layered mineral barrier. The solutions account for the two major mechanisms of subsurface contaminant migration, namely, advection and diffusion-dispersion. An example application using the proposed solutions and a numerical model illustrates how one multi-layered mineral barrier can be considered superior to another from a strictly hydro-dispersive viewpoint. The influence of partial saturation of the mineral barrier is investigated using a numerical solution to the Richards equation for unsaturated flow. It is emphasized that conclusions relative to the superiority of one multi-layered barrier, with respect to another, should not only consider hydro-dispersive aspects, but also other processes such as the mechanical and chemical evolutions of the different barrier components. Although such phenomena are poorly addressed by existing models, failure to take them into account, at least in a qualitative fashion, may lead to unconservative conclusions with respect to barrier equivalence.     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.     

Laboratory and field evaluation of measurement methods for one-hour exposures to O3, PM2.5, and CO.

While researchers have linked acute (less than 12-hr) ambient O3, PM2.5, and CO concentrations to a variety of adverse health effects, few studies have characterized short-term exposures to these air pollutants, in part due to the lack of sensitive, accurate, and precise sampling technologies. In this paper, we present results from the laboratory and field evaluation of several new (or modified) samplers used in the "roll-around" system (RAS), which was developed to measure 1-hr O3, PM2.5, and CO exposures simultaneously. All the field evaluation data were collected during two sampling seasons: the summer of 1998 and the winter of 1999. To measure 1-hr O3 exposures, a new active O3 sampler was developed that uses two nitrite-coated filters to measure O3 concentrations. Laboratory chamber tests found that the active O3 sampler performed extremely well, with a collection efficiency of 0.96 that did not vary with temperature or relative humidity (RH). In field collocation comparisons with a reference UV photometric monitor, the active O3 sampler had an effective collection efficiency ranging between 0.92 and 0.96 and a precision for 1-hr measurements ranging between 4 and 6 parts per billion (ppb). The limits of detection (LOD) of this method were 9 ppb-hr for the chamber tests and approximtely 16 ppb-hr for the field comparison tests. PM2.5 and CO concentrations were measured using modified continuous monitors--the DustTrak and the Langan, respectively. A size-selective inlet and a Nafion dryer were placed upstream of the DustTrak inlet to remove particles with aerodynamic diameters greater than 2.5 microm and to dry particles prior to the measurements, respectively. During the field validation tests, the DustTrak consistently reported higher PM2.5 concentrations than those obtained by the collocated 12-hr PM2.5 PEM samples, by approximately a factor of 2. After the DustTrak response was corrected (correction factor of 2.07 in the summer and 2.02 in the winter), measurements obtained using these methods agreed well with R2 values of 0.87 in the summer and 0.81 in the winter. The results showed that the DustTrak can be used along with integrated measurements to measure the temporal and spatial variation in PM2.5 exposures. Finally, during the field validation tests, CO concentrations measured using the Langan were strongly correlated with those obtained using the reference method when the CO levels were above the LOD of the instrument [approximately 1 part per million (ppm)].     

Controlling mechanisms of aluminium in soil solution--an evaluation of 180 podzolic forest soils.

To monitor the level of soil acidification in the county of V?rmland in the middle west of Sweden 180 podzolic forest soils were investigated. Soil solutions from four horizons were obtained by centrifugation and the soil was sampled for a determination of the exchangeable pool by extraction. The concentrations of inorganic Al and its fraction of the total Al in solution were greater in the south of the county (up to 50%). The factors influencing the total Al and free inorganic Al3+ in the soil solutions were evaluated. Saturation indices (SI) for five different mineral phases were calculated but none implied equilibrium conditions. The relationships between pAl3+ and pH (in the pH range 4-6.2) gave slopes of about 1, which indicated that ion exchange/complexation reactions may be important for determining the Al3+ concentration in the B and C horizons. In the E horizon solutions complexation with soluble organic acids seemed to be the major factor which influenced the Al3+ activity. The influence of organic matter on Al solubility was supported by partial least square (PLS) regressions.     

First report on chlorinated pesticide deposition in a sediment core from a small lake in central Chile.

This paper presents a first report on chlorinated pesticide deposition analyzed through sedimentary records in a small mesotrophic lake (Chica de San Pedro) in central Chile. The sediment core was sliced and dated using 210Pb, 137Cs and pollen analyses. Organochlorine pesticides were analyzed by gas chromatography with electron capture detection (GC-ECD). From these results, pesticide deposition over the last 50 years was estimated. No pesticides were detected below the 1940 slice of the core. Concentrations were in the range 0.640-1.4 ng/g d.w. for total DDTs, 0.046-0.362 ng/g d.w. for lindane and 0.015-0.310 ng/g d.w. for alpha-hexachlorohexane. Highest concentrations of pp'DDT were found in 1993-1996 and higher concentrations of pp'-DDE and pp'-DDD were found in the seventies (1972-1978). Total organic carbon (TOC) normalized data were used for statistical analysis. Although significant correlation was observed between concentrations of DDE and DDD, no correlation was found for DDT, suggesting that it had a different source. Factorial analysis grouped DDE together with DDD, while DDT was grouped together with gamma- and alpha-HCH. Total DDT fluxes were highest during the 1970s, while those for HCHs have been increasing in the 1990s. In Chile, organochlorine compounds were banned in 1985, and the historical deposition patterns seem to indicate that such measures have been effective. On the other hand, results point out a relatively new occurrence of pp'-DDT in the watershed, but the source remains unknown.     

Photooxidation of the phenylazonaphthol AO20 on TIO2: kinetic and mechanistic investigations.

The results of the photocatalytic and photosensitized degradations of the monoazo dye AO20 in aqueous solution using suspended titanium dioxide are presented. Kinetic and mechanistic details have been elucidated using UV/Vis, FTIR and TCO techniques. It was proven that adsorption of dye molecules onto the support material is essential for the processes to be effective. Moreover, even if their mechanisms differ during the early stages, photocatalysis and photosensitization lead to very similar ultimate breakdown products. Indeed, the original dye anchored to the oxide surface systematically undergoes fast decomposition until it is transformed into CO2 or aliphatic acids (formic, acetic, oxalic acids), which react rather slowly with hydroxyl radicals or trapped holes.     

Fluoride accumulation in pasture forages and soils following long-term applications of phosphorus fertilisers.

Ingestion of soils with high fluoride (F) concentration may cause chronic fluorosis in grazing animals. Analysis of New Zealand pasture soils with long-term phosphorus (P) fertilisation histories showed that total surface soil (0-75 mm depth) F concentration increased up to 217-454 mg kg-1 with P fertiliser application. One-third to two-thirds of F applied in fertilisers resides in the top 75 mm soil depth. Pasture forage accumulation of F was low, and therefore, F intake by grazing animals through pasture consumption is expected to be much lower than F intake by soil ingestion. Ten annual applications of single superphosphate (30 and 60 kg P ha-1 year-1) to a Pallic Soil (Aeric Fragiaqualf) significantly increased total F and labile F (0.01 M CaCl2 extract) concentrations to 200 and 120 mm depths, respectively, of the 300 mm depth investigated. The mobility of F in the soil profile was similar to two other elements, P and cadmium derived from the fertiliser.