A laboratory technique for investigation of diffusion and transformation of volatile organic compounds in low permeability media

A laboratory diffusion cell technique that permits spatial and temporal estimates of porewater concentrations over short intervals suitable for estimation of effective diffusion coefficients (De) and degradation rate constants (k) of volatile organic compounds (VOCs) in saturated low permeability media is presented. The diffusion cell is a sealed cylinder containing vapour reservoirs for sampling, including a vapour reservoir source and an array of vapour-filled "mini-boreholes", which are maintained water- and sediment-free by slightly negative porewater pressures. The vapour reservoirs were sampled by Solid Phase Micro-Extraction (SPME), resulting in minimal disturbance to the experimental system. Porewater concentrations are estimated from the measured vapour concentrations. Experiments were conducted using a non-reactive medium and five VOCs with a range in partitioning properties. Calibration experiments showed that equilibrium partition coefficients could be used for calculating concentrations in the vapour reservoir source from concentrations in the SPME coating after a 1-min microextraction and that the reservoir concentration was insignificantly affected by sampling. However, equilibrium was not reached during the one-min extraction of the boreholes; the microextraction reduced the borehole vapour concentrations, leading to diffusion of VOCs from porewater into the vapour-filled borehole. Thus, empirical partitioning coefficients were required for the determination of porewater VOC concentrations. The experimental data and numerical modelling indicate masses extracted by SPME extraction are relatively small, with minimal perturbation on processes studied in diffusion experiments. This technique shows promise for laboratory investigation of diffusion and transformation processes in low permeability media.     

An application of the theory of kinematics of mixing to the study of tropospheric dispersion

The most common technique used for numerical simulations of tracer mixing is that of the numerical solution of the advection–diffusion equation with the unresolved fluxes parameterized using the similarity theory. Despite correct predictions of the overall directions of transport, models based on a numerical solution of the advection–diffusion equation lack sufficient accuracy to correctly reproduce the coupling of mixing with small scale processes which are sensitive to the microstructure of the tracer distribution. The objective of this paper is to revisit the basic formalism employed in numerical models used to investigate atmospheric tracers. The main mathematical method proposed here is the theory of kinematics of mixing which could be applied effectively for simulations of atmospheric transport processes. At the beginning of the paper, we introduce simple mathematical transformations in order to demonstrate how complex topological structures are created by mixing processes. These idealistic flow systems are essential to explain transport properties of much more complex three-dimensional geophysical flows. An example of the application of the kinematics of mixing to the analysis of tracer transport on a planetary scale is presented in the following sections. The complex filamentary structures simulated in the numerical experiment are evaluated using some commonly applied statistical measures in order to compare the results with the data published in the literature. The results of the experiment are also analysed with the help of simple conceptual models of fluid filaments. The microstructure of the tracer distribution introduced in the paper is essential to increase our understanding of atmospheric transport and to develop more realistic parameterizations of small-scale mixing. The presented results could also be used to improve calculations of the coupling between microphysical processes and tracer mixing.     

Uncertainty analysis of emission estimates in the RAINS integrated assessment model

Uncertainty is a critical issue for all models that attempt to quantify the necessary emission reductions that are required to meet environmental quality targets. This paper discusses a methodology specifically developed to analyse the uncertainties in the emission estimates with the regional air pollution information and simulation (RAINS) integrated assessment model, considering the uncertainties in the model parameters themselves. Overall, it was found that a typical range of uncertainties for modeled national emissions of sulfur dioxide, nitrogen oxides and ammonia in Europe lies between 10 and 30%. In general, the uncertainties are strongly dependent on the potential for error compensation. This compensation potential is larger (and uncertainties are smaller) if calculated emissions are composed of a larger number of equal-sized source categories, where the errors in input parameters are not correlated with each other. Thus, estimates of the national total emissions are generally more certain than estimates of sectoral emissions. A sensitivity analysis with respect to the uncertainty in input parameters showed that the actual uncertainties are critically influenced by the specific situation (pollutant, year, country). However, the emission factor is an important contributor to the uncertainty in estimates of historical emissions, while uncertainty in the activity data dominates the future estimates.     

Water quality index applied to rivers in the Vistula river basin in Poland

Summary A new method of a water quality index has been proposed. The unit indices were determined from the values of individual parameters using continuous functions. The base for such functions were the four water quality classes used in Poland. The summarized WQI is the square root of the harmonic mean of squares of unit indices. Using this mean we have eliminated the use of weights of parameters. Parameters are divided into basic parameters (7) and other additional parameters (19). The additional parameter is considered only if its unit index is lower than WQI from basic parameters. For many measurements at one point the guaranteed WQI has been calculated. The points of WQI were connected and the curves of WQI along the river were obtained.A method of WQI calculating and preparation of WQI curves has been shown using as an example the Pilica river in Poland. The WQI was then calculated for 31 rivers in the Vistula river basin by measuring points.     

Legacies,socio-economic and biophysical processes and drivers: the case of future forest cover expansion in the Polish Carpathians and Swiss Alps

Mountain forest areas are key for providing a wide range of ecosystem services and are hot spots for land use change processes, in particular, increase in forest cover at the expense of mountain pastures and meadows. Mountain forest systems in eastern and western Europe have likely similar future socio-economic situations but significantly different socio-economic history. Using a scenario-based land use modelling approach (Dyna-CLUE framework) we model three scenarios (trend, liberalisation and self-sufficiency) of future land use in the Polish Carpathians and the Swiss Alps, focussing on forest cover change. We find that forest cover increase can be expected to continue in European mountainous regions under all likely scenarios, limited only by relatively strict policy interventions. Biophysical factors, rather than socio-economic ones, are key for defining the suitability for, and therefore likely locations of future forest cover, but land use legacy plays a very important role in the spatial patterns of future forest cover, particularly in eastern Europe.

     

Ozone recovery as seen in perspective of the Dobson spectrophotometer measurements at Belsk (52°N, 21°E) in the period 1963–2008

The total ozone monthly means derived from measurements by the Dobson spectrophotometer at Belsk (52°N, 21°E) and satellite observations over central and midlatitudinal Europe are analyzed for the long-term changes between 1995 and 2008. Standard explanatory variables representing physical and chemical processes known to influence the ozone distribution are considered. The potential proxies are: atmospheric loading by the ozone depleting substances characterized by the equivalent effective stratospheric chlorine (EESC) time series, various drivers of ozone dynamical variability including solar cycle, teleconnection patterns, temperature at 50 hPa, and pressure at the tropopause level. The multivariate adaptive regression splines (MARS) methodology is used to find optimal set of the explanatory variables and shape of the anthropogenic trend curve. Following options for the trend curve are examined: proportional to EESC, piecewise linear (with the turning points in 1980 and 1995), and selected from a smooth curve fit to the total ozone time series having “natural variations” removed. Statistical estimates and their uncertainties are calculated using block bootstrapping. The analyses indicate that ozone over Belsk, in central Europe, and in midlatitudinal Europe reaches at least first stage of recovery as defined by the World Meteorological Organization: a statistically significant reduction in the rate of decline. Model using the EESC time series as a proxy for the anthropogenic trend pattern yields even the second stage, i.e., a positive trend in time series that remains after removal dynamical signal from the analyzed data. Substantial seasonal dependent long-term ozone oscillations by the dynamical drivers are revealed causing estimation of the ozone recovery time even more uncertain.     

Discrete and time-integrated sampling for chromium load calculations in a watershed with an impoundment reservoir at an exceptionally low water level

Instantaneous (discrete) and time-integrated (composed) samples were collected during a 19-week period in a watershed impacted by discontinuous discharges from local tanneries (Carpathians Mountains, Poland). Existence of the impoundment reservoir in this watershed allowed investigation of its role in chromium transport. In collected samples, dissolved and particulate chromium concentrations were measured to apportion both loads. This study has demonstrated that the impoundment reservoir retains not only particulate but also a dissolved form of chromium and its efficiency reaches 74–94 %. Sampling results proved that chromium contamination in the investigated river is variable and discontinuous. Discrete sampling can lead to an underestimation of chromium contamination level (up to 78 %), especially when illegal/unexpected discharges occur in the watershed. A discrete sampling regime also produces less reliable data for contaminant budget calculations, especially in sites where strong variability of contamination is anticipated, while at the output from reservoirs, the load can be reasonably estimated using this mode of sampling.     

Internal and External Factors Influencing Time-Related Injury Risk in Continuous Shift Work

Time-related accident risk in shift work may be attributed to internal factors, such as fatigue, level of performance, sleep propensity, and to some external factors, like shift system, physical and social environment. Six hundred and sixty-eight events in the metallurgical industry have been analysed in terms of time of day, time on task, consecutive day of the shift block, day of the week, and season.

The injury rate was similar on all shifts but more severe accidents happened in the nighttime. Somewhat more injuries occurred in the second half of the shift, in the second part of a shift block, and in summer compared with winter. There were fewer injuries at weekends.     

Solid-Phase Microextraction As A Tool for Studying Volatile Compounds in Frog Skin

Solid-phase microextraction (SPME) is an effective technique for studying frog volatile secretions. Its primary advantage is in its application to sampling live animals. the ability to sample an organism over an extended period allows changes in an individual's chemical signature to be determined. the presence of eucalyptol in the skin secretion of Ewing's tree frog, Litoria ewingi, was used to assess the effectiveness of SPME in sampling frog volatiles. Rapid sample times coupled with the polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre provided the best signal/noise ratio for the majority of frog volatiles analysed, and importantly resulted in the least amount of stress to the animals involved.     

Torpor at high ambient temperature in a neotropical didelphid,the grey short-tailed opossum (Monodelphis domestica)

The grey short-tailed opossum, Monodelphis domestica, has been an established research animal for more than five decades, but relatively, little is known about its thermophysiology. Here we studied core body temperature (T _b) and metabolic rate (MR) of female adult M. domestica housed in the laboratory at an ambient temperature (T _a) of 26 °C. In expanding previous reports, the average recorded core T _b of M. domestica was 34.3 °C. The T _b of an individual M. domestica can drop below 30 °C (minimal T _b: 28.6 °C) accompanied by a reduction in MR of up to 52 % even while having ad libitum access to food. These findings demonstrate for the first time the presence of spontaneous torpor in M. domestica. Metabolic suppression at relatively high T _a and T _b furthermore broadens our perspective on the use of torpor as a metabolic strategy not just restricted to cold climates.