Fast and Living Ring-Opening Polymerization of l-Lactide Initiated with In-situ–Generated Calcium Alkoxides

The ring-opening polymerization of l-lactide with calcium alkoxides generated in-situ from bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] and 2-propanol are presented. The polymerization in THF at room temperature proceeds rapidly and in a living manner, giving poly(l-lactide)s of controlled molecular weight, low polydispersity, and tailored end-functionalities. Kinetic studies show the absence of an induction period and a pseudo-first order rate constant of 6.41 L mol^–1 min^–1, which is significantly higher than for related Y₅(-O)(O ⁱ Pr)_13– or aluminum alkoxide-initiated polymerizations. The initiation involves a two-step process: (1) alcoholysis of bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] to give the corresponding calcium alkoxide and (2) ring-opening of l-lactide via acyl-oxygen cleavage and insertion into the calcium-alkoxide bond. In the presence of excess alcohol, fast and reversible exchange between free alcohol molecules and coordinated alkoxide ligands takes place. This allows tuning of the poly(l-lactide) molecular weight over a wide range.     

Monitoring and Modelling of Ammonia Concentrations and Deposition in Agricultural Areas of The Netherlands

Passive samplers were used from 1996 to 1999 in a dense network to monitorthe concentrations of ammonia in air, in four agricultural areas in The Netherlands. To show representative patterns, sampling was not made within 50 m of livestock buildings and stores. The concentration of ammonia varies typically between 10 and 40 g m^-3 within a few kilometres in these areas. The interpretation of the measurements was supported by calculations with OPS, a Lagrangian dispersion model. Model calculations were based on a high-resolution database that included estimates of the ammonia emission of each farm in the area and emissions from surface application of manure at a 250 × 250 m scale. The model underestimated the observed ammonia concentrations by nearly a factor of two over most of the area. This result was attributed to underestimation of the ammonia emission in the models. And the ammonia emissions from field application of manure seem to be seriously underestimated. A detailed analysis of model results and measurements showed that the observed decrease of the ammonia concentration in the study period was partly due to changes in meteorological conditions during the study period and partly due to the reduced amount of manure applied in 1998.     

NITRATE CONCENTRATIONS IN GROUNDWATER BENEATH A BEEF CATTLE FEEDLOT1

ABSTRACT. A study of nitrate concentration in the groundwater beneath a beef cattle feedlot near Central City, Nebraska was started in 1968. An intensive 3-day pumping study was conducted at the feedlot at the start of 1970 irrigation system. Little nitrate concentration was found in the ground-water coming from beneath the feedlot. Pumping caused a slight increase in nitrate concentration over the average concentration for the previous 2 years.     

Decision Tree Algorithm for Detection of Spatial Processes in Landscape Transformation

The conversion of landscapes by human activities results in widespread changes in landscape spatial structure. Regardless of the type of land conversion, there appears to be a limited number of common spatial configurations that result from such land transformation processes. Some of these configurations are considered optimal or more desirable than others. Based on pattern geometry, we define ten processes responsible for pattern change: aggregation, attrition, creation, deformation, dissection, enlargement, fragmentation, perforation, shift, and shrinkage. A novelty in this contribution is the inclusion of transformation processes causing expansion of the land cover of interest. Consequently, we propose a decision tree algorithm that enables detection of these processes, based on three parameters that have to be determined before and after the transformation of the landscape: area, perimeter length, and number of patches of the focal landscape class. As an example, the decision tree algorithm is applied to determine the transformation processes of three divergent land cover change scenarios: deciduous woodland degradation in Cadiz Township (Wisconsin, USA) 1831–1950, canopy gap formation in a terra firme rain forest at the Tiputini Biodiversity Station (Amazonian Ecuador) 1997–1998, and forest regrowth in Petersham Township (Massachusetts, USA) 1830–1985. The examples signal the importance of the temporal resolution of the data, since long-term pattern conversions can be subdivided in stadia in which particular pattern components are altered by specific transformation processes.     

Seasonal variation of herbicide concentrations in prairie farm dugouts

Prairie farm dugouts are frequently constructed for use as potable water sources. Consequently, cumulative pesticide inputs via atmospheric deposition and surface runoff may constitute a risk to human health. Since, relative to other pesticides, herbicides are used in greatest amount on the Canadian prairies, herbicide concentrations were intensively monitored in three dugouts over three growing seasons. Herbicides were detected in the water of all three dugouts each growing season which may reflect cumulative inputs from atmospheric and surface processes over the lifetimes of the dugouts, which varied from 11 to 22 yr. Detections, which were not continuous, tended to be seasonal in nature. During the 3-yr study, detections were most frequent during the spring application period and late fall following dugout turnover. Between these periods, herbicide concentrations generally decreased to below detection limits. The reappearance of herbicides in the dugout water during fall turnover and in concentrations generally greater than those present during the spring application period suggest that, under appropriate environmental conditions, the bottom sediments may act as a source of herbicides to the water column. In general, herbicide inputs due to deposition of application drift did not result in detectable concentrations of herbicides in the dugouts. In the only year that winter samples were monitored, herbicides were also detected during ice cover. On the basis of monthly sampling over each growing season, median concentrations of 9 of the 10 herbicides monitored were less than 0.05 microg L(-1). The exception, 2,4-D, which has been used extensively on the Canadian prairies for more than 50 yr and in greatest amounts, was the most frequently detected herbicide. In no case did herbicide concentrations exceed Canadian drinking water guidelines; however, on occasion maximum herbicide concentrations did exceed aquatic life and irrigation water guidelines.     

Quantitative determination of volatile organic compounds in indoor dust using gas chromatography-UV spectrometry

A novel technique, gas chromatography-UV spectrometry (GC-UV), was used to quantify volatile organic compounds (VOCs) in settled dust from 389 residences in Sweden. The dust samples were thermally desorbed in an inert atmosphere and evaporated compounds were concentrated by solid phase micro extraction and separated by capillary GC. Eluting compounds were then detected, identified, and quantified using a diode array UV spectrophotometer. Altogether, 28 compounds were quantified in each sample; 24 of these were found in more than 50% of the samples. The compounds found in highest concentrations were saturated aldehydes (C5-C10), furfuryl alcohol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2-furaldehyde, and benzaldehyde. Alkenals were also found, notably 2-butenal (crotonaldehyde), 2-methyl-propenal (methacrolein), hexenal, heptenal, octenal, and nonenal. The concentrations of each of the 28 compounds ranged between two to three orders of magnitude, or even more. These results demonstrate the presence of a number of VOCs in indoor dust, and provide, for the first time, a quantitative determination of these compounds in a larger number of dust samples from residents. The findings also illustrate the potential use of GC-UV for analysing volatile compounds in indoor dust, some of which are potential irritants (to the skin, eyes or respiratory system) if present at higher concentrations. The potential use of GC-UV for improving survey and control of the human exposure to particle-bound irritants and other chemicals is inferred.     

Geophysical methods in radon risk studies

The results of the studies presented in the paper have shown that in the Upper Silesian Region in Poland, radon indoor concentration levels depend first of all on the geological structure of the subsurface layers. The essential factors influencing radon migration ability are the mining-induced transformations of a rock mass. In some cases, significant variations of radon potential have been found at sites featuring similar geological structures and experiencing comparable mining effects. To find out the causes of these variations, studies involving geophysical methods such as electrical resistivity profiling (PE) and electrical resisitivity sounding (VES) were used. These studies have shown that the measurements made using the electrical resistivity method can be helpful in evaluating radon potential of both the tectonically disturbed areas and the mining-transformed ones.     

Emissions from small-scale energy production using co-combustion of biofuel and the dry fraction of household waste

In sparsely populated rural areas, recycling of household waste might not always be the most environmentally advantageous solution due to the total amount of transport involved. In this study, an alternative approach to recycling has been tested using efficient small-scale biofuel boilers for co-combustion of biofuel and high-energy waste. The dry combustible fraction of source-sorted household waste was mixed with the energy crop reed canary-grass (Phalaris Arundinacea L.), and combusted in both a 5-kW pilot scale reactor and a biofuel boiler with 140-180 kW output capacity, in the form of pellets and briquettes, respectively. The chlorine content of the waste fraction was 0.2%, most of which originated from plastics. The HCl emissions exceeded levels stipulated in new EU-directives, but levels of equal magnitude were also generated from combustion of the pure biofuel. Addition of waste to the biofuel did not give any apparent increase in emissions of organic compounds. Dioxin levels were close to stipulated limits. With further refinement of combustion equipment, small-scale co-combustion systems have the potential to comply with emission regulations.     

Evaluation of oxidation stability of lignite humic substances by DSC induction period measurement

The stability of lignite humic acids and four regenerated humic acids was estimated by employing differential scanning calorimetry. Induction period for the oxidative decomposition of humic matter was calculated from non-isothermal measurements at six different rates of heating. To simulate the gradual evolution history of humic acids, different intensities of oxidation attack by nitric acid on the original lignite was used. Experimental data showed higher stability of natural humic acids in the temperature range where the decomposition step occurred. On the other hand, extrapolation to lower temperatures and calculated kinetic parameters did not correspond to the order observed at higher temperatures. An oscillating trend of calculated parameters of the two proposed parts of stability was observed, which agreed with data concerning regenerated humic acids production. The approach applied in this work represents a rapid and useful method for evaluation of organic matter stability.