The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

Preparation and Properties of Starch/Nanosilicate Layer/Polycaprolactone Composites

Starch nanocomposites have been prepared using mineral clay. Montmorillonite, kaolin and a surface-modified montmorillonite by dimethyl (hydrogenated tallow alkyl) ammonium cation were used. Starch-g-PCL nanocomposites have been prepared with graft polymerization through in situ ring-opening polymerization of ε-caprolactone in the presence of starch, Sn(Oct)₂ (Tin(II) 2-ethyl hexanoate) as an initiator/catalyst and silicate layers. In fact, the related composites were prepared in solution method, bulk polymerization and in situ polymerization methods with introducing the mineral clay. The effect of kind of clay on d-spacing of silicate layers was investigated and the obtained nanocomposites were analyzed using X-ray diffraction. The obtained compounds were characterized by Fourier transform infrared (FT-IR). Morphology of the prepared nanocomposites was investigated using scanning electron microscopy and DSC enhanced the study of thermal behaviour of the prepared composite compounds.     

The behaviour of ashes and heavy metals during the co-combustion of sewage sludges in a fluidised bed

Co-combustion tests of dry sewage sludges with coal were performed in a pilot bubbling FBC aiming at the characterization of ashes and determining the behaviour of heavy metals in the process. The tests showed compliance with the regulatory levels as far as heavy metal emissions were concerned. The bottom ashes, which accounted for about 70% of the total ash production, were obtained in a granular form, with diameters ranging from 0.5 to 4 mm. The heavy metals were distributed in ashes obtained from different locations of the installation and their concentrations were found to vary depending on the location of capture. The increase in heavy metals content in bottom ashes was not found to lead to higher leachability and ecotoxicity compared to sewage sludges, suggesting that there could be opportunities for their further use. Mercury suffered vaporisation inside the reactor, thus leaving bottom ashes free of contamination by it. However, there was observed a strong retention of mercury in cyclone ashes due to the presence of unburned carbon which probably acted as an adsorbent. The effluent mercury was also found to be mostly associated with the particulate fraction, being less than 20% emitted in gaseous forms. The results suggested that the combustion of the sewage sludge could successfully be carried out and the amount of unburned carbon leaving the combustor but captured in cyclone was large enough to ensure substantial retention of mercury at low temperatures, hence could contribute to an improvement of the mercury release which still remains an issue of great concern to resolve during combustion of waste materials.     

Mobility control: How injected surfactants and biostimulants may be forced into low‐permeability units

Recovering dense nonaqueous‐phase liquid (DNAPL) remains one of the most difficult problems facing the remediation industry. Still, the most common method of recovering DNAPL is to physically remove the contaminants using common technologies such as total fluids recovery pumps, vacuum systems, and “pump‐and‐treat.” Increased DNAPL removal can be attained using surfactants to mobilize and/or solubilize the pollutants. However, very little is understood of the methods developed by petroleum engineers beginning in the 1960s to overcome by‐passed, low‐permeability zones in heterogeneous oil reservoirs. By injecting or causing the formation of viscous fluids in the subsurface, petroleum engineers caused increased in‐situ pressures that forced fluid flow into low permeability units as well as the higher permeability thief zones. Polymer flooding involves injecting a viscous aqueous polymer solution into the contaminated aquifer. Foam flooding involves injecting surfactant to decontaminate the high‐permeability zones and then periodic pulses of air to cause a temporary viscous foam to form in the high‐permeable zones after all DNAPL is removed. Later surfactant pulses are directed by the foam into unswept low‐permeable units. These methods have been applied to DNAPL removal using surfactants but they can also be applied to the injection of bio‐amendments into low‐permeability zones still requiring continued remediation. Here we discuss the principles of mobility control as practiced in an alluvial aquifer contaminated with chlorinated solvent and coal tar DNAPLs as well as some field results. © 2003 Wiley Periodicals, Inc.     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Alfalfa rapidly remediates excess inorganic nitrogen at a fertilizer spill site

By 19%, standard remediation techniques had significantly reduced the concentration of nitrate nitrogen (NO3- -N) in local ground water at the site of a 1989 anhydrous ammonia spill, but NO3- -N concentrations in portions of the site still exceeded the public drinking water standard. Our objective was to determine whether local soil and ground water quality could be improved with alfalfa (Medicago sativa L.). A 3-yr study was conducted in replicated plots (24 by 30 m) located hydrologically upgradient of the ground water under the spill site. Three alfalfa entries ['Agate', Ineffective Agate (a non-N2-fixing elite germplasm similar to Agate), and MWNC-4 (an experimental germplasm)] were seeded in the spring of 1996. Corn (Zea mays L.) or wheat (Triticum aestivum L.) was seeded adjacent to the alfalfa each year. Crops were irrigated with N-containing ground water to meet water demand. During the 3-yr period, about 540 kg of inorganic N was removed from the aquifer through irrigation of 4.9 million L water. Cumulative N removal from the site over 3 yr was 972 kg N ha(-1) in Ineffective Agate alfalfa hay, compared with 287 kg N ha(-1) for the annual cereal grain. Soil solution NO3- concentrations were reduced to low and stable levels by alfalfa, but were more variable under the annual crops. Ground water quality improved, as evidenced by irrigation water N concentration. We do not know how much N was removed by the N2-fixing alfalfas, but it appears that either fixing or non-N2-fixing alfalfa will effectively remove inorganic N from N-affected sites.     

IMPACTS OF CLIMATE CHANGE ON MISSOURI RWER BASIN WATER YIELD1

ABSTRACT: Water from the Missouri River Basin is used for multiple purposes. The climatic change of doubling the atmospheric carbon dioxide may produce dramatic water yield changes across the basin. Estimated changes in basin water yield from doubled CO₂ climate were simulated using a Regional Climate Model (RegCM) and a physically based rainfall‐runoff model. RegCM output from a five‐year, equilibrium climate simulation at twice present CO₂ levels was compared to a similar present‐day climate run to extract monthly changes in meteorologic variables needed by the hydrologic model. These changes, simulated on a 50‐km grid, were matched at a commensurate scale to the 310 subbasin in the rainfall‐runoff model climate change impact analysis. The Soil and Water Assessment Tool (SWAT) rainfall‐runoff model was used in this study. The climate changes were applied to the 1965 to 1989 historic period. Overall water yield at the mouth of the Basin decreased by 10 to 20 percent during spring and summer months, but increased during fall and winter. Yields generally decreased in the southern portions of the basin but increased in the northern reaches. Northern subbasin yields increased up to 80 percent: equivalent to 1.3 cm of runoff on an annual basis.     

Development and Adoption of a Simple Nonpoint Source Pollution Model for Port Phillip Bay,Australia

New computing tools and approaches allow tailored development of software to meet the needs of environmental managers. The processes required for such tailoring fit well with adaptive management concepts where, as knowledge and system understanding develop among managers, the software can be developed or replaced to match. This paper reports on development and adoption of a simple nonpoint source pollution modeling tool, including technical aspects of data support for modeling and social aspects of software design. The software, named FILTER, used a unit load model to generate expected pollutant loads from subcatchments of Port Phillip Bay, Australia. Monitoring data were used for calibration to modify the delivery of generated pollutants to receiving waters. Spatial, tabular, and charting software components were used to provide alternative forms of output visualization. FILTER was developed using a process that resulted in manager-stakeholders taking responsibility for setting of model parameter values and operation of the user interface, thereby encouraging uptake. The inclusive development process, tailoring of the software to manager needs and styles of usage, and matching of model complexity to data and knowledge, resulted in a successful application that has become the current agreed system representation among disparate stakeholder organizations.     

Transforming open mining pits into fish farms: Moving towards sustainability

The legacy of mining activities has typically been land ‘returned to wildlife’, or, at some sites, degraded to such an extent that it is unsuitable for any alternate use. Progress towards sustainability is made when value is added in terms of the ecological, social and economic well‐being of the community. In keeping with the principles of sustainable development, the innovative use of flooded open pits and tailings impoundments as commercial, recreational or ornamental fish farms should be considered in some locations, as it could make a significant contribution to the social equity, economic vitality and environmental integrity of mining communities. This article highlights the growing significance of aquaculture and explores the benefits and barriers to transforming flooded pits and impoundments into aquaculture operations. Among other benefits, aquaculture may provide a much‐needed source of revenue, employment and, in some cases, food to communities impacted by mine closure. Further, aquaculture in a controlled closed environment may be more acceptable to critics of fish farming who are concerned about fish escapes and viral transmissions to wild populations. Despite the potential benefits, aquaculture in flooded pits and impoundments is not without its complications — it requires a site‐specific design approach that must consider issues ranging from metals uptake by fish, to the long‐term viability of the aquatic system as fish habitat, to the overall contribution of aquaculture to sustainability.     

Temporal and Spatial Relationships Between Watershed Land Use and Salt Marsh Disturbance in a Pacific Estuary

Historical and recent remote sensing data can be used to address temporal and spatial relationships between upland land cover and downstream vegetation response at the watershed scale. This is demonstrated for sub-watersheds draining into Elkhorn Slough, California, where salt marsh habitat has diminished because of the formation of sediment fans that support woody riparian vegetation. Multiple regression models were used to examine which land cover variables and physical properties of the watershed most influenced sediment fan size within 23 sub-watersheds (1.4 ha to 200 ha). Model explanatory power increased (adjusted R(2) = 0.94 vs. 0.75) among large sub-watersheds (>10 ha) and historical watershed variables, such as average farmland slope, flowpath slope, and flowpath distance between farmland and marsh, were significant. It was also possible to explain the increase in riparian vegetation by historical watershed variables for the larger sub-watersheds. Sub-watershed area is the overriding physical characteristic influencing the extent of sedimentation in a salt marsh, while percent cover of agricultural land use is the most influential land cover variable. The results also reveal that salt marsh recovery depends on relative cover of different land use classes in the watershed, with greater chances of recovery associated with less intensive agriculture. This research reveals a potential delay between watershed impacts and wetland response that can be best revealed when conducting multi-temporal analyses on larger watersheds.