Comparison of constant volume balloons, model trajectories and tracer transport during ETEX

In the field phases of the European Tracer EXperiment (ETEX), an inert tracer was released for 12 h into the atmosphere and samples taken at several locations downwind. During the same time, several Constant Volume Balloons (CVB) (10 and 6 for ETEX first and second release, respectively) were launched into different altitudes and followed as far as 21–188 km, to indicate the initial dispersion directions of the tracer puff. A model simulating the CVB behaviour in hydrostatic meso-scale model forecasts is applied to ETEX data to demonstrate its capability to predict the tracer puff mean axis over long distances (−2000 km). CVB model results are first compared to air parcels trajectories and 2D (i.e. isentropic, isobaric and isodensity) trajectories. Then they are compared to the measured CVB trajectories and finally to the tracer puff trajectories. As expected, the CVB model and isodensity model trajectories are found to be identical. The 16 CVBs calculated trajectories nearly overlap the real ones over 21–188 km with mean absolute horizontal transport deviations less than 20 km (average value of 8.2 km). The corresponding relative transport deviations are less than 45% with an average value of 20.6%. Better predictions are obtained for the ETEX second release. During the 60 h following ETEX’s first release start, the simulated CVBs are mainly found in the area of the maximum surface concentrations of the released tracer, up to 2000 km. Up to 36 h after ETEX second tracer release start, the simulated CVB trajectories predict well the mean axis of the tracer puff, but failed later.     

Evaluation of the Meteo-France response in ETEX release 1

During ETEX Meteo-France applied part of its emergency response system for critical events developped in the framework of the World Meteorological Organization environmental emergency response program. The atmospheric transport model used to forecast the evolution of a passive tracer is an eulerian model called MEDIA. In real time this model is driven by meteorological data from ARPEGE, the operational numerical weather prediction model available at the Meteo-France operation center. The overall evaluation of the results show that the model can reproduce the cloud displacement, but there exists a stretching in the transport direction. In the ATMES-II phase, the results are closer to the observations when meteorological data from the European Center for Medium range Weather Forecast are used. A simulation using analyzed meteorological data from ARPEGE every 6 h slightly improve the results comparing with the real-time experiment. All the simulations we performed reveal that the quality of the atmospheric transport model is strongly dependent on the quality of the driving numerical weather prediction model.     

Validation of the lagrangian particle dispersion model FLEXPART against large-scale tracer experiment data

A comprehensive validation of FLEXPART, a recently developed Lagrangian particle dispersion model based on meteorological data from the European Centre for Medium-Range Weather Forecasts, is described in this paper. Measurement data from three large-scale tracer experiments, the Cross-Appalachian Tracer Experiment (CAPTEX), the Across North America Tracer Experiment (ANATEX) and the European Tracer Experiment (ETEX) are used for this purpose. The evaluation is based entirely on comparisons of model results and measurements paired in space and time. It is found that some of the statistical parameters often used for model validation are extremely sensitive to small measurement errors and should not be used in future studies. 40 cases of tracer dispersion are studied, allowing a validation of the model performance under a variety of different meteorological conditions. The model usually performs very well under undisturbed meteorological conditions, but it is less skilful in the presence of fronts. The two ETEX cases reveal the full range of the model’s skill, with the first one being among the best cases studied, and the second one being, by far, the worst. The model performance in terms of the statistical parameters used stays rather constant with time over the periods (up to 117 h) studied here. It is shown that the method used to estimate the concentrations at the receptor locations has a significant effect on the evaluation results. The vertical wind component sometimes has a large influence on the model results, but on the average only a slight improvement over simulations which neglect the vertical wind can be demonstrated. Subgrid variability of mixing heights is important and must be accounted for.     

Mesoscale influence on long-range transport — evidence from ETEX modelling and observations

During the first European Tracer Experiment (ETEX) tracer gas was released from a site in Brittany, France, and subsequently observed over a range of 2000 km. Hourly measurements were taken at the National Environmental Research Institute (NERI) located at Risø, Denmark, using two measurement techniques. At this location, the observed concentration time series shows a double-peak structure occurring between two and three days after the release. By using the Danish Emergency Response Model of the Atmosphere (DERMA), which is developed at the Danish Meteorological Institute (DMI), simulations of the dispersion of the tracer gas have been performed. Using numerical weather-prediction data from the European Centre for Medium-Range Weather Forecast (ECMWF) by DERMA, the arrival time of the tracer is quite well predicted, so also is the duration of the passage of the plume, but the double-peak structure is not reproduced. However, using higher-resolution data from the DMI version of the HIgh Resolution Limited Area Model (DMI-HIRLAM), DERMA reproduces the observed structure very well. The double-peak structure is caused by the influence of a mesoscale anti-cyclonic eddy on the tracer gas plume about one day earlier.     

Bulgarian emergency response models–validation against ETEX first release

In the paper, the performance of two Bulgarian dispersion models is tested against European Tracer Experiment (ETEX) first release data base. The first one is the LED puff model which was the core of the Bulgarian Emergency Response System during all releases of ETEX. The second one is the newly created Eulerian dispersion model EMAP. These models have two important features: they are PC-oriented and they use quite a limited amount of input meteorological information. First, a number of runs with various source configurations are made on meteorological data produced by ECMWF. The aim of these runs is to verify the models’ ability to simulate reliably ETEX first release. To this end, a set of statistical criteria selected in ATMES (Atmospheric Transport Models Evaluation Study, see Klug et al., 1992 are used. The best runs for both models are obtained when the source is presented as a column towering from the ground to heights of 400–700 m. These runs took part in the second phase of ETEX (ETEX-II), the so called ATMES-type exercise where EMAP ranked ninth and LED - fourteenth among 34 models. Here, additional sets of EMAP are presented where in the first run the value of the horizontal diffusion coefficient is varied and in the other runs different meteorological data sets are tested. The results obtained from the first run show that the values of K_h=4–6×10⁴ m² s^-1 produce fields which fit experimental data best. The other sets of runs show that the higher the frequency of the meteorological data, the better the simulation. The results can be improved by linear interpolation of the meteorological parameters with time, the best fitting obtained with interpolation at each time step.     

Validation of the UK Met. Office’s name model against the ETEX dataset

The ETEX 1 data set has been used to assess the performance of the UK Met Office’s long-range dispersion model NAME. In terms of emergency response modelling the model performed well, successfully predicting the overall spread and timing of the plume across Europe. However, in common with most other models, NAME overpredicted the observed concentrations. This is in contrast with other NAME validation studies which indicate either no significant bias or a tendency to underpredict concentrations. This suggests the reasons for overpredicting are specific to the ETEX situation. Explanations include inadequate vertical diffusion or transport, possible venting by convective activity, and experimental errors. An assessment of a range of advection schemes of varying complexity indicated no clear advantage, at present, in using more sophisticated random walk techniques at long range, a simple diffusion coefficient based scheme providing some of the best results. A brief look is also taken at a simulation of the more problematical ETEX 2 release.     

Solute transport in crystalline rocks at Äspö — I: Geological basis and model calibration

Water-conducting faults and fractures were studied in the granite-hosted Äspö Hard Rock Laboratory (SE Sweden). On a scale of decametres and larger, steeply dipping faults dominate and contain a variety of different fault rocks (mylonites, cataclasites, fault gouges). On a smaller scale, somewhat less regular fracture patterns were found. Conceptual models of the fault and fracture geometries and of the properties of rock types adjacent to fractures were derived and used as input for the modelling of in situ dipole tracer tests that were conducted in the framework of the Tracer Retention Understanding Experiment (TRUE-1) on a scale of metres. After the identification of all relevant transport and retardation processes, blind predictions of the breakthroughs of conservative to moderately sorbing tracers were calculated and then compared with the experimental data. This paper provides the geological basis and model calibration, while the predictive and inverse modelling work is the topic of the companion paper [J. Contam. Hydrol. 61 (2003) 175].The TRUE-1 experimental volume is highly fractured and contains the same types of fault rocks and alterations as on the decametric scale. The experimental flow field was modelled on the basis of a 2D-streamtube formalism with an underlying homogeneous and isotropic transmissivity field. Tracer transport was modelled using the dual porosity medium approach, which is linked to the flow model by the flow porosity. Given the substantial pumping rates in the extraction borehole, the transport domain has a maximum width of a few centimetres only. It is concluded that both the uncertainty with regard to the length of individual fractures and the detailed geometry of the network along the flowpath between injection and extraction boreholes are not critical because flow is largely one-dimensional, whether through a single fracture or a network. Process identification and model calibration were based on a single uranine breakthrough (test PDT3), which clearly showed that matrix diffusion had to be included in the model even over the short experimental time scales, evidenced by a characteristic shape of the trailing edge of the breakthrough curve. Using the geological information and therefore considering limited matrix diffusion into a thin fault gouge horizon resulted in a good fit to the experiment. On the other hand, fresh granite was found not to interact noticeably with the tracers over the time scales of the experiments.While fracture-filling gouge materials are very efficient in retarding tracers over short periods of time (hours–days), their volume is very small and, with time progressing, retardation will be dominated by altered wall rock and, finally, by fresh granite. In such rocks, both porosity (and therefore the effective diffusion coefficient) and sorption K_ds are more than one order of magnitude smaller compared to fault gouge, thus indicating that long-term retardation is expected to occur but to be less pronounced.     

Meteorological conditions at the release site during the two tracer experiments

The state of the boundary layer at the release site during the two tracer experiments is described, based on measurements of atmospheric turbulence carried out by a sonic anemometer, profiles of horizontal and vertical wind by a SODAR as well as frequent radiosonde releases. The boundary layer height is derived from radiosoundings, modelled and discussed. The study is meant as background for discussions of the tracer behaviour near the release site, and possible influence of the local meteorology at the release site on the long-range dispersion. The difference in the initial meso-meteorological conditions between the two experiments is discussed and some of its consequences for the dispersion of the released tracer are clarified. It is concluded that the first experiment is well suited for validation of long-range transport and dispersion models, whereas the second experiment calls for further model development. It is concluded that the micrometeorological measurements are very important as background information for the understanding of plume behaviour on small as well as long scales.     

The influence of south Foehn on the ozone distribution in the Alpine Rhine valley—results from the MAP field phase

During the Mesoscale Alpine Programme (MAP) special observation period (SOP) between 7 September and 15 November 1999, ground-based and airborne measurements have been conducted in the Rhine valley south of the Lake of Constance to investigate the unstationary aspects of Foehn and related phenomena, like the impact of Foehn on the ozone concentrations in the valley. Foehn events occurred with above-average frequency and high diversity. Foehn induced ozone peaks in October and November are found to be much lower than the September Foehn case of the period. An inversion layer in the lake area with ozone concentrations below 10 ppb often shields the monitoring stations from the Foehn air aloft. Trajectory calculations for the Foehn period between 19 and 24 October 1999 reveal that the Foehn air originated from below 1 to 1.5 km above the Po Basin and the Mediterranean Sea. Tethered balloon soundings in the source area south of the Alps, ozone measurements at the mountain station Jungfraujoch (3580 m a.s.l.) and airborne measurements across the Alpine crests reveal that the ozone levels found in the Foehn air correspond to the concentrations just above the mixing height in the Po Basin and are transported across the Alpine crest within the lowest flow layer.     

Trends and sources of particulate matter in the Superstition Wilderness using air trajectory and aerosol cluster analysis

Ambient aerosols adversely affect human health and visibility and impact climate. Identification of sources of particulate matter and its precursors is necessary for developing control strategies. The goal of this research is to utilize long-term speciated particulate matter data and back-trajectory cluster analyses to determine trends and sources of particulate matter in the Superstition Wilderness, a rural area east of Phoenix, Arizona. Twenty-four hour back-trajectories were calculated for every hour of every 24-h particulate matter sample obtained by IMPROVE from 1991 to 2004. Days that included back-trajectories with considerable spatial variance were excluded from further analyses. To minimize uncertainties inherent in single trajectories, all calculated trajectories for each sampling day were averaged to represent the air mass sampled during that day. Cluster analysis of trajectories identified four unique regions, including a region with Phoenix, a region with copper smelters, and one with coal-fired power plants. Yearly averages of sulfate, nitrate, soil, and carbon concentrations were calculated for each region. Statistically significant trends in species concentrations by region and independent of region and differences in concentrations between regions were examined.Sulfate concentrations from the region with smelters were higher than other regions but decreased during the study period. Emissions data from the smelters indicate that much of the sulfate from the region was due to the smelters. The overall 2.2% year⁻¹ decrease in sulfate concentrations at TNM is likely due to decreased emissions from the copper smelters. A 3.6% year⁻¹ increase in nitrate concentrations was driven largely by increasing NO_x concentrations from Phoenix and to a lesser extent the region southwest of the site which includes Tucson and suburban/urban areas between Phoenix and Tucson. Soil concentrations were higher from regions with deserts than the region without desert. This method could not identify trends or source regions of carbonaceous aerosols at this site.     

Occurrence of monoethylmercury in the Florida Everglades: Identification and verification

A few studies have reported the occurrence of monoethylmercury (CH₃CH₂Hg⁺) in the natural environment, but further verification is needed due to the lack of direct evidence and/or uncertainty in analytical procedures. Various analytical techniques were employed to verify the occurrence of CH₃CH₂Hg⁺ in soil of the Florida Everglades. The identity of CH₃CH₂Hg⁺ in Everglades soil was clarified, for the first time, by GC/MS. The employment of the recently developed aqueous phenylation-purge-and-trap-GC coupled with ICPMS confirmed that the detected CH₃CH₂Hg⁺ was not a misidentification of CH₃SHg⁺. Stable isotope-tracer experiments further indicated that the detected CH₃CH₂Hg⁺ indeed originated from Everglades soil and was not an analytical artifact. All these evidence clearly confirmed the occurrence of CH₃CH₂Hg⁺ in Everglades soil, presumably as a consequence of ethylation occurring in this wetland. The prevalence of CH₃CH₂Hg⁺ in Everglades soil suggests that ethylation could play an important role in the biogeochemical cycling of Hg.     

Perfluorocarbon background concentrations in Europe

Five studies of the background level of several perfluorocarbon compounds in Europe are here presented together with measurements from the European Tracer Experiment (ETEX). The tracers used during the two ETEX tracer releases were the perfluorocarbons (PFCs); perfluoromethylcyclohexane (C₇F₁₄, PMCH) and perfluoromethylcyclopentane (C₆F₁₂, PMCP). Their background concentrations were detected by using both passive and active sampling techniques, to define the spatial and temporal variation of the PFCs over Europe. Also the background variations of four isomers of the PFC compound perfluorodimethylcyclohexane (C₈F₁₆, PDCH) were studied. The results were compared to other PFC tracer studies in the U.S.A. and Europe. The mean and median values of the measured PFCs were found to vary slightly and randomly in space and time. They were found to be higher and to have a larger standard deviation than the measurements from the American studies. The background concentrations were still found to be low and stable enough for PFCs to be highly suitable for use in tracer studies. The following concentrations were found: PMCP; 4.6±0.3 fl ℓ^-1, PMCH: 4.6±0.8 fl ℓ^-1, ocPDCH: 0.96±0.33 fl ℓ^-1, mtPDCH: 9.3±0.8 fl ℓ^-1, mcPDCH: 8.8±0.8 fl ℓ^-1, ptPDCH: 6.1±0.8 fl ℓ^-1. A study of the correlation between the measured PFC compounds showed a significant correlation between most of the compounds, which indicate that there are no major PFC sources in Europe.     

改性蔗渣焚烧灰去除糖蜜酒精废液中硫酸根

以改性蔗渣灰（MBA）为吸附剂,通过单因素实验,等温吸附模型拟合实验和正交实验,探讨了MBA去除糖蜜酒精废液的高浓度硫酸根离子的实验条件。结果表明,当MBA粒径60目,投加量为3 g·（25 mL）-1,反应温度45℃,pH为4.2,反应时间50 min时,溶液中的硫酸盐去除效果最优。等温吸附模型拟合结果表明,Langmuir模型更适合拟合该过程,MBA去除硫酸根离的反应为单分子层吸附。正交实验次优反应条件可以确定为：废液浓度为稀释15倍,MBA投加量3.0 g·（25 mL）-1,MBA粒径80目,反应时间1 h,反应温度为35℃。经验证,硫酸根离子的去除率达到88.86%。     

一种固态磷酸根离子选择电极

针对检测水中磷酸根离子浓度的问题,研究了一种以玻碳为基底的固态磷酸根离子选择电极。在一定条件下采用循环伏安法聚合硫酸钴和硫酸钠的混合溶液,并根据正交实验得出电极最佳制备条件。采用直接电位法测定电极性能指标,得到斜率为-41.7 mV,检测下限为6.3×10-5 mol·L-1,电极的线性响应范围在10-1~10-4 mol·L-1的固态磷酸根离子选择电极;电极具有较短的响应时间,很好的稳定性,对磷酸根的检测研究具有一定的意义。     

A multi-directional tracer test in the fractured Chalk aquifer of E. Yorkshire, UK

A multi-borehole radial tracer test has been conducted in the confined Chalk aquifer of E. Yorkshire, UK. Three different tracer dyes were injected into three injection boreholes and a central borehole, 25 m from the injection boreholes, was pumped at 330 m(3)/d for 8 days. The breakthrough curves show that initial breakthrough and peak times were fairly similar for all dyes but that recoveries varied markedly from 9 to 57%. The breakthrough curves show a steep rise to a peak and long tail, typical of dual porosity aquifers. The breakthrough curves were simulated using a 1D dual porosity model. Model input parameters were constrained to acceptable ranges determined from estimations of matrix porosity and diffusion coefficient, fracture spacing, initial breakthrough times and bulk transmissivity of the aquifer. The model gave equivalent hydraulic apertures for fractures in the range 363-384 microm, dispersivities of 1 to 5 m and matrix block sizes of 6 to 9 cm. Modelling suggests that matrix block size is the primary controlling parameter for solute transport in the aquifer, particularly for recovery. The observed breakthrough curves suggest results from single injection-borehole tracer tests in the Chalk may give initial breakthrough and peak times reasonably representative of the aquifer but that recovery is highly variable and sensitive to injection and abstraction borehole location. Consideration of aquifer heterogeneity suggests that high recoveries may be indicative of a high flow pathway adjacent, but not necessarily connected, to the injection and abstraction boreholes whereas low recoveries may indicate more distributed flow through many fractures of similar aperture.     

Diffusive partitioning tracer test for the quantification of nonaqueous phase liquid (NAPL) in the vadose zone: Performance evaluation for heterogeneous NAPL distribution

A partitioning tracer test based on gas-phase diffusion in the vadose zone yields estimates of the residual nonaqueous phase liquid (NAPL) saturation. The present paper investigates this technique further by studying diffusive tracer breakthrough curves in the vadose zone for a heterogeneous NAPL distribution. Tracer experiments were performed in a lysimeter with a horizontal layer of artificial kerosene embedded in unsaturated sand. Tracer disappearance curves at the injection point and tracer breakthrough curves at some distance from the injection point were measured inside and outside of the NAPL layer. A numerical code was used to generate independent model predictions based on the physicochemical sand, NAPL, and tracer properties. The measured and modeled tracer breakthrough curves were in good agreement confirming the validity of important modeling assumptions such as negligible sorption of chlorofluorocarbon (CFC) tracers to the uncontaminated sand and their fast reversible partitioning between the soil air and the NAPL phase. Subsequently, the model was used to investigate different configurations of NAPL contamination. The experimental and model results show that the tracer disappearance curves of a single-well diffusive partitioning tracer test (DPTT) are dominated by the near-field presence of NAPL around the tip of the soil gas probe. In contrast, breakthrough curves of inter-well tracer tests reflect the NAPL saturation in between the probes, although there is no unique interpretation of the tracer signals if the NAPL distribution is heterogeneous. Numerical modeling is useful for the planning of a DPTT application. Simulations suggest that several cubic meters of soil can be investigated with a single inter-well partitioning tracer test of 24-hour duration by placing the injection point in the center of the investigated soil volume and probes at up to 1 m distance for the monitoring of gaseous tracers.     

曝气对水平潜流人工湿地水力特性的影响

通过构建曝气及未曝气潜流人工湿地小试实验系统,以NaCl为示踪剂开展示踪实验,研究曝气对人工湿地水力特性的影响。实验结果表明,两对比系统均存在不同程度的短流及死区现象,短流主要发生在床体表层,而死区则存在于床体底层。其中未曝气人工湿地系统的流场分布不均匀现象较为严重,示踪剂滞留在床体底层难以回收,系统水力效率较低(0.56)。比较而言,由于气流对水体的扰动作用,曝气对人工湿地系统水力效率有明显改善作用,减缓了床体表层水流速度,提高了示踪剂回收率,缩小了死区的范围,曝气人工湿地系统的水力效率为0.75。