Betaine removal during thermo- and mesophilic aerobic batch biodegradation of beet molasses vinasse: influence of temperature and pH on the progress and efficiency of the process

The key issue in achieving a high extent of biodegradation of beet molasses vinasse is to establish the conditions for the assimilation of betaine, which is the main pollutant in this high-strength industrial effluent. In the present study, aerobic batch biodegradation was conducted over the temperature range of 27-63°C (step 9°C), at a pH of 6.5 and 8.0, using a mixed culture of bacteria of the genus Bacillus. Betaine was assimilated at 27-54°C and the pH of 8.0, as well as at 27-45°C and the pH of 6.5. The processes where betaine was assimilated produced a high BOD(5) removal, which exceeded 99.40% over the temperature range of 27-45°C at the pH of 8.0, as well as at 27°C and the pH of 6.5. Maximal COD removal (88.73%) was attained at 36°C and the pH of 6.5. The results indicate that the process can be applied on an industrial scale as the first step in the treatment of beet molasses vinasse.     

Fish assemblages composition in a natural, then regulated, stream: A quantitative long-term study

This paper tests the hypothesis how effectively fish assemblage composition was shaped by local climate changes and by engineering impact in 1989. This was possible due to the monitoring protocols of the present study, which allowed estimation of the magnitude of anthropogenic changes from changes naturally occurring in nature. Fish were sampled at the end of every growing season (October) for 23 years at five contiguous sites in a stream, before (1979-1988) and after (1989-2001) regulation. In each sample, six successive electrofishing passes were used to calculate the density and mean biomass for assemblage analysis using the Zippin model. During the study, the natural, meandering stream with pools, riffles, and a moderate canopy was modified into a straight stream of uniform width and depth, stripped of all vegetation. The output layer of a self-organizing map (SOM, the artificial neural network algorithm) applied in this study for site similarity analysis was partitioned into six subclusters placed in two main clusters. Subclusters in the upper part of the SOM were occupied chiefly by regulated stream samples and those in the lower part of the SOM by natural stream samples. Subclusters in the middle position, contained both natural (19) and regulated (20) samples in nearly equal proportion. In addition, the SOM contained one subcluster with sites only from the regulated period and another with only natural sites. Differences between subclusters were attributed to differences in climate, with some differences profound. Warming of the local weather, which became most evident in the 1990s, may have resulted in changes in fish assemblages. This is shown in the SOM, in which samples from the 1980s with cold years dominate the bottom of the SOM, whereas those from the 1990s and later are at the top. Subclusters dominated by regulated or natural sites were not always significantly different when the number of species and diversity indices were considered. Clear differences between the regulated and natural samples involved qualitative characteristics and mainly concerned assemblage composition. They were also confirmed by significant IndVal values (indicator species) and neither mixed subcluster contained important species in their assemblages.     

Molecular composition of leaves and stems of genetically modified Bt and near-isogenic non-Bt maize--characterization of lignin patterns

Transformation of crops, including maize (Zea mays L.), with the cry1Ab gene from Bacillus thuringiensis to combat lepidopteran pests results in pleiotropic effects regarding lignin biosynthesis. Lignin patterns in stems and leaves of two genetically modified Bt-maize varieties (Novelis T and Valmont T) were studied along with their non-Bt near-isolines (Nobilis and Prelude, respectively). Molecular-level based thermochemolysis using tetramethylammonium hydroxide (TMAH) in combination with gas chromatography-mass spectrometry (GC-MS) was used to quantitate the total lignin contents and to identify monomeric lignin subunits including p-hydroxyphenyl (P), guaiacyl (G), and syringyl (S) moieties. The results were supplemented and confirmed by cupric oxide oxidation. The stems of the transgenic lines had higher concentrations of total lignin than the respective isogenic lines: Valmont T/Prelude by 18% and Novelis T/Nobilis by 28%. In contrast, differences in the total lignin concentration of leaves between the transgenic and the respective near-isogenic lines were marginal. There were significant modifications in the ratio of p-hydroxyphenyl/guaiacyl/syringyl molecular marker units of stem lignin between transgenic and isogenic lines. The guaiacyl units (in particular the G18 marker) accounted chiefly for the higher total lignin contents in the transgenic lines. The leaf lignin patterns did not show significant differences in molecular markers between isogenic and transgenic lines. TMAH-induced thermochemolysis--conducted in both the on-line and off-line modes--provided detailed information on the molecular composition of lignin, thus proving superior to the established "wet chemistry" methods of lignin determination.     

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.     

Geostatistical 3-dimensional integration of measurements of soil magnetic susceptibility

In soil magnetometry, two types of measurements are usually performed. The first type is measurements performed on the soil surface, frequently using an MS2D sensor. The second type includes measurements of magnetic susceptibility carried out in the soil profile, usually to a depth of about 30 cm. Up to now, such measurement results were analyzed separately. However, it is possible and advantageous to integrate these two types of measurements. The goal of the study was to integrate measurements of magnetic susceptibility performed on the soil surface and in the soil profile. More specifically, the goal was to obtain 3-dimensional spatial distributions of magnetic susceptibility of the topsoil horizon. Results show that it is possible to effectively integrate measurements of magnetic susceptibility performed on the soil surface and in the soil profile. Moreover, the 3-dimensional spatial distribution that is obtained shows the magnetic susceptibility of the top 20 cm of soil, which includes the soil horizons where most of the heavy metals are accumulated. The analysis of such a spatial distribution can be very helpful in delineating areas where the heightened magnetic susceptibility is a result of the influence of anthropogenic pollution from those areas where it results from lithogenic origin. It is possible to investigate where the volumes of soil with heightened magnetic susceptibility are located in the soil profile and in this way investigate which characteristic type of soil profile it is.     

Investigation of a systematic offset in the measurement of organic carbon with a semicontinuous analyzer

Organic carbon (OC) was measured semicontinuously in laboratory experiments of steady-state secondary organic aerosol formed by hydrocarbon + nitrogen oxide irradiations. Examination of the mass of carbon measured on the filter for various sample volumes reveals a systematic offset that is not observed when performing an instrumental blank. These findings suggest that simple subtraction of instrumental blanks determined as the standard analysis without sample collection (i.e., by cycling the pump and valves yet filtering zero liters of air followed by routine chemical analysis) from measured concentrations may be inadequate. This may be especially true for samples collected through the filtration of small air volumes wherein the influence of the systematic offset is greatest. All of the experiments show that filtering a larger volume of air minimizes the influence of contributions from the systematic offset. Application of these results to measurements of ambient concentrations of carbonaceous aerosol suggests a need for collection of sufficient carbon mass to minimize the relative influence of the offset signal.     

Domestic sampling: exposure assessment to moth repellent products using ultrasonic extraction and capillary GC-MS

Moth repellent agents are considered major contributors to indoor air pollution. In this study, the chemical contamination of clothes due to their direct or indirect exposure to moth repellent agents such as p-dichlorobenzene, naphthalene and camphor were investigated. Cotton cloths were used as clothing simulant. They were analyzed using ultrasonic extraction followed by GC-MS analysis. Extrapolated results indicate that a regular cotton shirt indirectly exposed to these chemicals in a storage cabinet can contain up to 7, 3 and 7.5mg of p-dichlorobenzene, naphthalene and camphor, respectively, even after one-hour of airing. Passive sorptive sampling using polydimethylsiloxane-coated stir-bars and ultrasonic extraction followed by GC-MS analysis was used to monitor the concentration distribution in a wardrobe.     

Catalytic destruction of 1,2-dichlorobenzene on V2O5-WO3/Al2O3-TiO2 catalyst

Studies on the catalytic destruction of 1,2-dichlorobenzene were carried out on a specially constructed semi-technical equipment whose most important element was a catalytic reactor with a monolithic catalyst in the form of 150 x 150 x 100 mm cubes. A catalyst made from cordierite with an active layer composed of Al2O3 - 64 wt%, TiO2 - 26 wt%, V2O5 - 6.6 wt% and WO3 - 3.4 wt% was used. The reactor made it possible to carry out the process in the temperature range 150-350 degrees C, at variable catalyst loading and different velocities of gas flow through the reactor. The content of 1,2-dichlorobenzene in the air was analysed by a chromatographic method. A significant effect of catalyst loading and temperature on 1,2-dichlorobenzene destruction efficiency was observed and no effect of the linear flow velocity through the catalyst on o-dichlorobenzene destruction efficiency was reported. The applied vanadium-tungsten catalyst on a monolithic carrier made from TiO2/gamma-Al2O3 revealed very good activity that resulted in an over 80% efficiency of 1,2-dichlorobenzene destruction at the temperature around 250 degrees C at a very high catalyst loading reaching ca. 8200 h(-1). Additionally, in this study the kinetics of 1,2-dichlorobenzene decomposition was determined, specifying the order of reaction and dependence of the decomposition rate constant on temperature, using a simple power-rate law model.     

Quantification of carbon dioxide and methane emissions in urban areas: source apportionment based on atmospheric observations

Anthropogenic emissions of carbon dioxide (CO₂) and methane (CH₄) in the atmosphere constitute an important component of the related carbon budget. The main source of anthropogenic CO₂ is burning of fossil fuels, especially in densely populated areas. Similar emissions of CH₄ are associated with the agricultural sector, coal mining, and other human activities, such as waste management and storage and natural gas networks supplying methane to large urban, industrial centers. We discuss several methods aimed at characterizing and quantifying atmospheric loads and fluxes of CO₂ and CH₄ in Krakow, the second largest city in Poland. The methods are based on atmospheric observations of mixing ratios as well as isotopic composition of the investigated gases. Atmospheric mixing ratios of CO₂ and CH₄ were measured using gas chromatography (GC) and cavity ring-down spectroscopy (CRDS). The isotopic composition of CO₂ and CH₄ was analyzed using isotope ratio mass spectrometry (IRMS), accelerator mass spectrometry (AMS), and CRDS techniques. These data, combined with auxiliary information characterizing the intensity of vertical mixing in the lower atmosphere (height of the nocturnal boundary layer [NBL] and atmospheric ²²²Rn concentration), were further used to quantify emission rates of CO₂ and CH₄ in the urban atmosphere of Krakow. These methods provide an efficient way of quantifying surface emissions of major greenhouse gases originating from distributed sources, thus complementing the widely used bottom-up methodology based on emission statistics.

     

Nickel immobilization in ceramic matrix admixed with waste nickel hydroxide

WAXS examinations performed with nickel hydroxide samples heated to various temperatures showed that freshly settled wet nickel hydroxide sample contains some amount of crystalline beta-Ni(OH)(2) structure and its share increased when sample was dried during 3 weeks at ambient temperature. However, the share significantly decreased when the sample was dried at 110 degrees C and more so at 250 degrees C. Crystalline phase traces of Ni(OH)(2) disappeared after sample burning at 980 degrees C and instead the distinct presence of crystalline NiO was determined. The above samples were examined for solubility in stoichiometric amount of sulphuric acid diluted with water to pH 1.9 and 2.8. Solubility was determined by measuring nickel ion concentration in leachate by the AAS method. The dissolving rate was found to decrease with the rise of temperature to which the nickel hydroxide samples were heated. The solubility of Ni(OH)(2) sample burnt at 980 degrees C was undetectable during 90 h solubility-testing time likely due to its transformation into sparingly soluble crystalline NiO. The latter is considered to be the reason for effective immobilization of waste nickel hydroxide in ceramic prepared by blending with clay and sintering at 980 degrees C.