Fluorescence-based evidence for adsorptive binding of pyrene to effluent dissolved organic matter

Using fluorescence intensity measurements, pyrene interactions with different types of effluent dissolved organic matter (EDOM) originated from treated municipal wastewater are examined. Multiple observations show that fluorescence intensity of pyrene–EDOM solutions is non-linearly related to pyrene concentration, with distinct concave-up dependence. Testing the effect of pyrene concentration on fluorescence intensity of pyrene–EDOM solutions provides a tool to examine whether binding of an organic compound to EDOM follows linear or non-linear isotherm. Possible coupling between static and dynamic quenching effects was addressed while analyzing fluorescence data. Limited number of EDOM binding sites results in a non-linear binding isotherm such that the concept of pyrene “partitioning” between aqueous phase and “bulky” EDOM organic phase is hardly relevant. Maximal EDOM capacity for pyrene binding is estimated approximately as 0.1% w w⁻¹. Examination of the differences between the total fluorescence intensity of pyrene–EDOM solution and the fluorescence intensities of separated constituents (pyrene and EDOM) was used to illustrate the accumulation of pyrene–EDOM complexes and saturation of some EDOM binding sites. Strong interactions between pyrene and EDOM binding sites may result in pyrene distribution coefficients differing at least by a factor 3.5–7 at varying pyrene concentrations.     

Laboratory models to evaluate phytotoxicity of sulphadimethoxine on terrestrial plants

Antimicrobial drugs soil contamination is a possible side effect of spreading animal wastes from intensive farming on arable land: waste often contain persistent drugs (like sulphonamides) that pollute soil. In laboratory tests different crop plants and weeds demonstrated, on both synthetic medium and soil, toxicity and sulphadimethoxine bioaccumulation. These data suggest potential adverse implications for organisms higher up the food net, including humans. The increasingly used technique of'soil top dressing will impose the monitoring of antimicrobial contamination in arable lands and their crops, to protect natural ecosystems and consumer. A possible tool for this monitoring is the use of weeds that can constitute a “mesh” where antimicrobial contamination can be detected.     

Joint propagation of variability and imprecision in assessing the risk of groundwater contamination

Estimating risks of groundwater contamination often require schemes for representing and propagating uncertainties relative to model input parameters. The most popular method is the Monte Carlo method whereby cumulative probability distributions are randomly sampled in an iterative fashion. The shortcoming of the approach, however, arises when probability distributions are arbitrarily selected in situations where available information is incomplete or imprecise. In such situations, alternative modes of information representation can be used, for example the nested intervals known as “possibility distributions”. In practical situations of groundwater risk assessment, it is common that certain model parameters may be represented by single probability distributions (representing variability) because there are data to justify these distributions, while others are more faithfully represented by possibility distributions (representing imprecision) due to the partial nature of available information. This paper applies two recent methods, designed for the joint-propagation of variability and imprecision, to a groundwater contamination risk assessment. Results of the joint-propagation methods are compared to those obtained using both interval analysis and the Monte Carlo method with a hypothesis of stochastic independence between model parameters. The two joint-propagation methods provide results in the form of families of cumulative distributions of the probability of exceeding a certain value of groundwater concentration. These families are delimited by an upper cumulative distribution and a lower distribution respectively called Plausibility and Belief after evidence theory. Slight differences between the results of the two joint-propagation methods are explained by the different assumptions regarding parameter dependencies. Results highlight the point that non-conservative results may be obtained if single cumulative probability distributions are arbitrarily selected for model parameters in the face of imprecise information and the Monte Carlo method is used under the assumption of stochastic independence. The proposed joint-propagation methods provide upper and lower bounds for the probability of exceeding a tolerance threshold. As this may seem impractical in a risk-management context, it is proposed to introduce “a-posteriori subjectivity” (as opposed to the “a-priori subjectivity” introduced by the arbitrary selection of single probability distributions) by defining a single indicator of evidence as a weighted average of Plausibility and Belief, with weights to be defined according to the specific context.     

Norwegian Meteorological Institute’s real-time dispersion model snap (Severe Nuclear Accident Program): Runs for ETEX and ATMES II experiments with different meteorological input

The Norwegian Meteorological Institute (DNMI) has developed and implemented for operational use a real-time dispersion model Severe Nuclear Accident Program (SNAP) with capability for predicting concentrations and depositions of the radioactive debris from large accidental releases. SNAP has been closely linked to DNMI’s operational numerical weather prediction (NWP) models.How good are these predictions? Participation in ETEX has partly answered this question. DNMI used SNAP with LAM50S giving meteorological input for these real-time dispersion calculations. LAM50S Limited Area Model with 50 km grid squareswas DNMI’s operational NWP model in 1994 when ETEX took place.In this article we report on how SNAP performed in the first of the ETEX releases in near-real-time mode, using LAM50S—and in hindcast mode for ATMES II, using “ECMWF 1995: ETEX Data set (ATMES II)”as meteorological input data. These two input data sets came from NWP models with quite different characteristics but with similar resolution in time and space.The results from these dispersion simulations matched closely. Deviations early in the simulation period shrank to insignificant differences later on. Since both input data sets were based on “weather analysis” and had similar resolution in space and time, SNAP described the dispersion of the released material very similar in these two simulations.     

Three long-range transport models compared to the ETEX experiment: a performance study

For operational or research purposes (dispersion computations of radioactive effluents during nuclear emergency situations, simulations of chemical pollution in the vicinity of thermal power plants), different models of passive dispersion in the atmosphere have been developed at the Environment Department of EDF’s R and D Division. This report presents the comparison of the performances of three such models: DIFTRA (lagrangian puff model, with operational goal), DIFEUL (three dimensional eulerian) and DIFPAR (Monte Carlo particle model) for the simulation of the first ETEX release, an international tracer campaign during which a passive tracer cloud has been followed over Europe. The results obtained in this study give model vs. experience differences of the same order as the model vs. experience differences observed during an international model comparison experiment using data of the Chernobyl release, the ATMES exercise. In addition to the standard statistical scores used in the evaluation of the performances of the transport models two asymmetric scores (in contradistinction with the Figure of Merit in Space) are proposed: “efficiency” and “power”. Their aim is to separate the two manners in which a model may be wrong: by predicting presence of pollutant while none is measured or conversely predicting absence when pollutant is actually detected.     

Comparison of solubility databases used for HLW performance assessment

Elemental solubility limits are employed in many performance assessment studies of the disposal of high-level radioactive waste. A comparison of solubility databases used in a number of recent assessments from Canada, Finland, Japan, Sweden, Switzerland and the U.S.A. is presented. Despite similarities in the chemical conditions under which such solubilities are defined, there are very large ranges in the values selected for most elements (several orders of magnitude). In some cases, differences in solubilities can be attributed to differences in the thermodynamic databases used but, due to generally incomplete documentation, both of such databases and the criteria for data selection, detailed analysis of the reason for such discrepancies is precluded. A key factor, however, is the fairly subjective choice of the solid phase considered to be “solubility-limiting”. Procedures are recommended which would increase the transparency of solubility database compilation in future analyses.     

Air ventilation impacts of the “wall effect” resulting from the alignment of high-rise buildings

The objective of this study is to investigate the air ventilation impacts of the so called “wall effect” caused by the alignment of high-rise buildings in complex building clusters. The research method employs the numerical algorithm of computational fluid dynamics (CFD – FLUENT) to simulate the steady-state wind field in a typical Hong Kong urban setting and investigate pollutant dispersion inside the street canyon utilizing a pollutant transport model. The model settings of validation study were accomplished by comparing the simulation wind field around a single building block to wind tunnel data. The results revealed that our model simulation is fairly close to the wind tunnel measurements. In this paper, a typical dense building distribution in Hong Kong with 2 incident wind directions (0° and 22.5°) is studied. Two performance indicators are used to quantify the air ventilation impacts, namely the velocity ratio (VR) and the retention time (T_r) of pollutants at the street level. The results indicated that the velocity ratio at 2 m above ground was reduced 40% and retention time of pollutants increased 80% inside the street canyon when high-rise buildings with 4 times height of the street canyon were aligned as a “wall” upstream. While this reduction of air ventilation was anticipated, the magnitude is significant and this result clearly has important implications for building and urban planning.     

Testing kernel density reconstruction for Lagrangian photochemical modelling

In recent years, a number of pioneering works have shown as Lagrangian models can be of great interest when dealing with photochemistry, provided that special care is given in the reconstruction of chemicals concentration in the atmosphere. Density reconstruction can be performed through the so-called “box counting” method: an Eulerian grid for chemistry is introduced and density is computed counting particles in each box. In this way one of the main advantages of the Lagrangian approach, the grid independence, is lost. In this paper, a new approach to Lagrangian photochemical modelling is investigated and the chemical module of the Photochemical Lagrangian Particle Model (PLPM) is described and fully tested for stability, reliability and computational weight. Photochemical reactions are treated in PLPM by means of the complex chemical mechanism SAPRC90 and four density reconstruction methods have been developed, based on the kernel density estimator approach, in order to obtain grid-free accurate concentrations.     

Wind flow simulation over greater Athens area with highly resolved topography

The code system containing the DELTA and the ADREA codes has been developed at the National Centre of Scientific Research (NCSR) “DEMOKRITOS” and performs mesoscale wind field calculations over terrains of high complexity. The code system follows a particular technique of discretization, according to which the ground can be treated with a resolution higher than the one used in the atmosphere. This technique, called “the high-resolution-ground-low-resolution-air” concept, offers to the code system the capability to reliably simulate the thermal air-ground interaction processes, keeping at the same time the computation storage and duration in reasonable levels. The above code system was applied to a high-resol ution representation of the Attika district, within a domain of 72 × 72 × 6.125 km³. Mesoscale wind field calculations were made within the framework of the APSIS Phase-A Intercomparison Exercise, using the atmospheric radiosonde and surface data of 25 May 1990. In this particular day, the greater Athens area was dominated by the daytime thermally driven local systems, generated along the coastlines of the peninsula. The application of the DELTA-ADREA system reproduced the above mesoscale influences and exhibited a favourable agreement with observations.     

Uranium transfer phenomena in rock matrix: petrophysical and geochemical study of El Berrocal experimental site, Spain

The role played by the petrophysical characteristics of the rock matrix in the radioelement transfer phenomena through the geosphere is considered. The aim of this paper is to correlate information provided by the microcrack network, mineralogy and U-micromapping studies which can be used to quantify the extent of radioelement migration/retention in the granite. This study is part of an interdisciplinary research project on the El Berrocal site (Spain), which forms part of the R & D Programme “Management and Disposal of Radioactive Waste” of the Commission of the European Communities.The experimental procedure combines complementary microscopic techniques: polarizing light, fluorescence, confocal laser scanning, acoustic, scanning electron microscopy and uranium-induced fission-track micromapping. All of these techniques are applied for quantifying the rock matrix characteristics.Data on preferential fissure zones in relation to mineralogy, and the correlation between these data and uranium microdistribution are obtained. These results are discussed in terms of radionuclide mobility and can be used, with other information, for evaluating the retardation capacity of the crystalline rock matrix around a high-level radioactive waste repository.     

Comparison of various sampling methods for PCDDs and PCDFs in stack gas

There have been discussions about how complete PCDDs and PCDFs are sampled from stack gas of waste combustion plants by various sampling methods. In Germany, at present, a sampling method is used, which was first proposed by Nottrodt et al.¹, consisting of a filter device, condenser, and an absorption train. Since this sampling procedure complicates sampling and analysis, we compared this “standard procedure” with a “dilution method”, where only a filter, impregnated with paraffin, is used as trapping device, and also tested the effectiveness of XAD-2 as an adsorption trap.

As standard procedure the standard train was always used in parallel to other sampling methods. The results of four parallel sampling periods confirmed, that comparable results are obtained, when parallel sampling is carried out with the standard train.

The result of our investigation can be summarized as follows: The total emission of PCDDs and PCDFs determined by different sampling procedures varies only insignificantly. This means that sampling and analysis for PCDDs and PCDFs in stack gas could be simplified considerably.     

Levels, profile and pattern of PCDDs and PCDFs in samples related to the production and use of chlorine

Analyses of sludge from graphite electrodes used in the chloralkali process show total levels of PCDFs as high as 650000 pg/g sludge. The levels of tetra-, penta-and hexaCDFs were found to be approximately the same. The levels for the corresponding PCDDs were below the detection level. The dominating congeners within each group are the toxic 2,3,7,8-substituted PCDFs at levels of 340000 pg/g, This typical pattern, called the “chloralkali pattern” can also be found in soil samples taken at another chloralkali plant. The typical pattern can also be identified in a solution of ferric chloride. Traces of “chloralkali pattern” are identified in a sludge sample from the drinking water purification plant, the source for PCDFs in the sludge is unknown.     

Estimation and validation of PM2.5/PM10 exhaust and non-exhaust emission factors for practical street pollution modelling

In order to carry out efficient traffic and air quality management, validated models and PM emission estimates are needed. This paper compares current available emission factor estimates for PM₁₀ and PM_2.5 from emission databases and different emission models, and validates these against eight high quality street pollution measurements in Denmark, Sweden, Germany, Finland and Austria.The data sets show large variation of the PM concentration and emission factors with season and with location. Consistently at all roads the PM₁₀ and PM_2.5 emission factors are lower in the summer month than the rest of the year. For example, PM₁₀ emission factors are in average 5–45% lower during the month 6–10 compared to the annual average.The range of observed total emission factors (including non-exhaust emissions) for the different sites during summer conditions are 80–130 mg km⁻¹ for PM₁₀, 30–60 mg km⁻¹ for PM_2.5 and 20–50 mg km⁻¹ for the exhaust emissions.We present two different strategies regarding modelling of PM emissions: (1) For Nordic conditions with strong seasonal variations due to studded tyres and the use of sand/salt as anti-skid treatment a time varying emission model is needed. An empirical model accounting for these Nordic conditions was previously developed in Sweden. (2) For other roads with a less pronounced seasonal variation (e.g. in Denmark, Germany, Austria) methods using a constant emission factor maybe appropriate. Two models are presented here.Further, we apply the different emission models to data sets outside the original countries. For example, we apply the “Swedish” model for two streets without studded tyre usage and the “German” model for Nordic data sets. The “Swedish” empirical model performs best for streets with studded tyre use, but was not able to improve the correlation versus measurements in comparison to using constant emission factors for the Danish side. The “German” method performed well for the streets without clear seasonal variation and reproduces the summer conditions for streets with pronounced seasonal variation. However, the seasonal variation of PM emission factors can be important even for countries not using studded tyres, e.g. in areas with cold weather and snow events using sand and de-icing materials. Here a constant emission factor probably will under-estimate the 90-percentiles and therefore a time varying emission model need to be used or developed for such areas.All emission factor models consistently indicate that a large part (about 50–85% depending on the location) of the total PM₁₀ emissions originates from non-exhaust emissions. This implies that reduction measures for the exhaust part of the vehicle emissions will only have a limited effect on ambient PM₁₀ levels.     

Toxicity tests with luminescent photobacteria and quantitative structure activity relationships for nitroparaffins

EC₅₀ values of different nitroparaffins were determined by a photobacterium phosphoreum toxicity test. Octanol/water partition coefficients were determined by a reversed phase HPLC method. From these experimental data quantitative structure activity relationships were deduced which point to a dependence of toxicity on a “form factor” that includes the number of methyl and methylene groups in a molecule. The hypothesis will be formulated that the specific effects depend on the number of methylgroups and an equation for specific effects is given.     

Kinetic study of the removal of dimethyl phthalate from an aqueous solution using an anion exchange resin

Phthalate acid esters are becoming an important class of pollutants in wastewaters. This study addresses the kinetics of removal of dimethyl phthalate (DMP) using the anion exchange resin D201-OH from an aqueous solution. The effects of various factors on the removal rate and efficiency were investigated. An overall initial removal rate (OIRR) law and a pseudo first-order kinetic (PFOK) model were also developed. The internal diffusion of DMP within the resin phase of D201-OH is the rate-controlling step. Optimization of the particle size and pore structure of the resin D201-OH, the DMP concentration, and the reaction temperature can improve the DMP removal rate. The hydrolysis reaction of DMP catalyzed by D201-OH indicates an overall reaction order of 1.76, a value that is between the first order and the second order. The apparent activation energy of the reaction is 34.6 kJ/mol, which is below the homogeneous alkaline hydrolysis activation energy of 44.3 kJ/mol. The OIRR law can quantify the initial removal rate under different conditions. The results also show that the theoretical DMP removal efficiency predicted by the PFOK model agrees well with the experimentally determined values. Our research provides valuable insights into the primary parameters influencing the kinetic process, which enables a focused improvement in the removal or hydrolysis rate for similar processes.     

Acid aerosols in the Pittsburgh Metropolitan area

This article presents data on ambient concentrations of selected acidic aerosols at four existing monitoring sites in the Pittsburgh PA metropolitan area. The data were collected by staff of the Allegheny County Health Department, Division of Air Quality during the summer and fall of 1993. The sampling protocol was focused on obtaining 24 h-average ammonia, ammonium, acidic sulfates, and particle strong acids data on a 2 to 3 day cycle. The data were obtained using Harvard University School of Public Health's “Short-HEADS” annular denuder sampling train. The Pittsburgh area is of interest because it is downwind of a major regional source of sulfur and nitrogen emissions from coal-burning power plants: the Ohio River Valley. The data presented here indicate that ground-level concentrations of acidic aerosols in Pittsburgh are highly correlated spatially and that many pollutants are higher on days when ground-level wind direction vectors indicate that wind is coming from the southwest rather than from the Pittsburgh source area itself. The monitoring site that is most upwind of the Pittsburgh source area – South Fayette – has particle strong acid levels about twice those of sites closer in to the Pittsburgh central business district.     

Perspectives of a large scale environmental survey for chlorinated dioxins: overview and soil data

On November 5, 1984, The Dow Chemical Company issued a report entitled: “Point Sources and Environmental Levels of 2378-TCDD on the Midland Plant Site of The Dow Chemical Company and in the City of Midland, Michigan.” This report is based upon the efforts of a 22-person task force who dedicated approx. 21 months of effort to the generation and analysis of over 6000 analytical data points regarding specific CDD/CDF concentrations in the four basic environmental elements of air, earth, fire (incineration), and water. A summarization of this study will be presented which includes methodology, analytical QA-QC criteria, and representative soil analyses, as they pertain to the survey conclusions.