Novel Biobased Polyurethanes Synthesized from Soybean Phosphate Ester Polyols: Thermomechanical Properties Evaluations

Biobased polyurethanes from soybean oil–derived polyols and polymeric diphenylmethane diisocyanate (pMDI) are prepared and their thermomechanical properties are studied and evaluated. The cross-linked biobased polyurethanes being prepared from soy phosphate ester polyols with hydroxyl contents ranging from 122 to 145 mg KOH/g and pMDI within 5 min of reaction time at 150°C in absence of any catalyst show cross-linking densities ranging from 1.8 × 10³ to 3.0 × 10³ M/m³, whereas glass transition temperatures vary from approximately 69 to 82°C. The loss factor (tan ) curves show single peaks for all these biobased polyurethanes, thus indicating a single-phase system. The storage moduli (G) at 30°C range from 4 × 10⁸ to 1.3 × 10⁹ Pa. Upon postcure at 150°C, the thermomechanical properties can be optimized. Cross-link densities are improved significantly for hydroxyl content of 139 and 145 mg KOH/g at curing time of 24 h. Similarly, glass transition temperature (T_g) and storage moduli around and after T_g are increased. Meanwhile, tan intensities decrease as result of restricted chain mobility. Longer exposure time (24 h) induces thermal degradation, as evidenced by thermogravimetric analysis (TGA). The dynamic mechanical (DMA) analysis shows that postcure at 100°C for times exceeding 24 h also leads to improved properties. However, cross-linking densities are lower compared to postcure carried out at 150°C.     

The Synthesis and FTIR, Kinetics and TG/DTG/DTA Study of Inter Penetrating Polymer Networks (IPNs) Derived from Polyurethanes of Glycerol Modified Castor Oil and Cardanol Based Dyes

Interpenetrating polymer networks from agricultural products such as glycerol modified castor oil polyurethanes and cardanol based dyes have not been extensively studied so far. Such polymers were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate as cross-linker. Characterizations of these polymers were performed by Fourier Transform infra red spectra and thermal analysis techniques such as thermogravimetric analysis, derivative thermogravimetry and differential thermal analysis. The kinetic parameters such as activation energies and orders of reaction were estimated by using Freeman?CAnderson??s method. The effects of changes in polyurethane to dye monomer weight ratio and NCO/OH molar ratio of polyurethanes on the properties of such polymers were studied.     

Effects of Lime and Ash Treatments on DOC Fractions and Low Molecular Weight Organic Acids in Soil Solutions of Acidified Podzolic Soils

Dissolved organic carbon (DOC) fractions and different low molecular weight organic acids (LMWOAs) were determined in soil solutions from two lime or ash treated Norway spruce sites in the south of Sweden. At Hasslöv, 3.45 t ha^-1 or 8.75 t ha^-1 dolomite were applied 15 years before sampling. Horröd was treated with 4.28 t ha^-1 ash and 3.25 t ha^-1 dolomite and sampled four years later. Propionate (7–268 M) and malonate (2–34 M) were the LMWOAsfound in the highest concentrations at Hasslöv. Two other LMWOAs dominated at Horröd, namely citrate (18–64 M)and fumarate (5–31 M). The differences in concentration of most of the determined LMWOAs at Hasslöv were significantly increased due to treatment. The LMWOAs comprised between 1.1–6.3% of the DOC at Hasslöv and 4.5–17.6% at Horröd. At Hasslöv normally 3–10% of the total acidity (TA) was due to LMWOAs and the average specific buffer capacity was 74 ± 22 mmol mol^-1C.The total DOC concentration in the mor layer solution was 16 mM for the dolomite treated plots compared to 10 mM at the untreated plot. A major part of the increase in DOC at the treated plots apparently had a hydrophobic character and was of high molecular weight corresponding to 3–10 kDa. The concentration of DOC < 1 kDa in the control and treated plots was similar.     

A Conceptual Model of Spatially Heterogeneous Nitrogen Leaching from a Welsh Moorland Catchment

Soil- and stream-water data from the Plynlimon research area, mid-Wales, have been used to develop a conceptual model of spatial variations in nitrogen (N) leaching within moorland catchments. Extensive peats, in both hilltop and valley locations, are considered near-complete sinks for inorganic N, but leach the most dissolved organic nitrogen (DON). Peaty mineral soils on hillslopes also retain inorganic N within upper organic horizons, but a proportion percolates into mineral horizons as nitrate (NO ₃ ^– ), either through incomplete immobilisation in the organic layer, or in water bypassing the organic soil matrix via macropores. This NO ₃ ^– reaches the stream where mineral soilwaters discharge (via matrix throughflow or pipeflow) directly to the drainage network, or via small N-enriched flush wetlands. NO ₃ ^– in hillslope waters discharging into larger valley wetlands will be removed before reaching the stream. A concept of catchment nitrate leaching zones is proposed, whereby most stream NO ₃ ^– derives from localised areas of mineral soil hillslope draining directly to the stream; the extent of these zones within a catchment may thus determine its overall susceptibility to elevated surface water NO ₃ ^– concentrations.     

The release of nitrous oxide from the intertidal zones of two European estuaries in response to increased ammonium and nitrate loading

Nitrous oxide (N₂O) release and denitrification rates were investigated from the intertidal saltmarsh and mudflats of two European river estuaries, the Couesnon in Normandy, France and the Torridge in Devon, UK. Sediment cores and water were collected from each study site and incubated for 72 h in tidal simulation chambers. Gas samples were collected at 6 and 12 h intervals from the chambers during incubation. From these N₂O emission rates were calculated. The greatest rates for both N₂O production and denitrification were measured from saltmarsh cores. These were 1032 mol N₂O m^–2 day^–1 and 2518 mol N₂ m^–2 day^–1, respectively, from the Couesnon and 109 mol N₂O m^–2 day^–1 and 303 mol N₂ m^–2 day^–1 from the Torridge. A strong positive correlation was apparent with N₂O emission rates and ammonium concentration in the sediment, nitrate concentration in floodwater and sediment aerobicity.     

Preparation conditions and swelling equilibria of biodegradable hydrogels prepared from microbial poly(γ-glutamic acid) and poly(ε-lysine)

Biodegradable hydrogels prepared by -irradiation from microbial poly(amino acid)s are reviewed. pH-sensitive hydrogels were prepared by means of -irradiation of poly(-glutamic acid) (PGA) produced byBacillus subtilis IFO3335 and poly(-lysine) (PL) produced byStreptomyces albulus in aqueous solutions. The preparation conditions, swelling equilibria, hydrolytic degradation, and enzymatic degradation of these hydrogels were studied. A hydrogel with a wide variety of swelling behaviors has been produced by -irradiation from a mixture solution of PGA and PL.Paper presented at the 4th International Workshop on Biodegradable Plastics and Polymers, October 11–14, 1995, Durham, New Hampshire, USA.     

Air Pollution Zones and Harmful Pollution Levels of Alkaline Dust for Plants

For characterisation of landscapes in north-eastern Estoniaaffected by alkaline oil shale fly ash and cement dust the zonation-method based on average annual (C _y) and short-termconcentrations of pollutants in the air was used, as well as on deposition loads of dust and Ca²⁺. In the overground layer of atmosphere the zones with different air pollution loads were distinguished. A comparative analysis of pollution zones characteristics and biomonitoring data revealed that for sensitive lichen the dangerous level of alkaline dust in the air, introducingthe degradation of Sphagnum sp. at the level of C _y of dust 10–20 g m^-3 and at 0.5–1 hr maximums 100–150 g m^-3. For Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) this limited concentration (decline of growth parameters) of cement dust is correspondingly following: 30–50 g m^-3 and 150–500 g m^-3, in case of fly ash the limit level of C _y amounting 100 g m^-3. Daily deposition load of Ca²⁺ should not exceed approximately 4.5–15 mg m^-2 for lichen; for conifers the harmful pollution load is higher – >22 mg m^-2.     

An Automated Wet Deposition System to Compare the Effects of Reduced and Oxidised N on Ombrotrophic Bog Species: Practical Considerations

Critical N loads for ombrotrophic bogs, which often contain rare and N-sensitive plants (especially those in lower plant groups: lichens, mosses and liverworts), are based on very few experimental data from measured, low background N deposition areas. Additionally the relative effects of reduced versus oxidised N are largely unknown. This paper describes an automated field exposure system (30 km S. of Edinburgh, Scotland) for treating ombrotrophic bog vegetation with fine droplets of oxidised N (NaNO₃) and reduced N (NH₄Cl). Whim Moss exists in an area of low ambient N deposition (ca. 8 kg N ha^–1 y^–1), the sources and quantification of which are described. The wet N treatment system is run continuously, and is controlled/activated by wind speed and rainfall to provide a unique simulation of real world treatment patterns (no rain=no treatment). Simulated precipitation is supplied at ionic concentrations below4mMin rainwater collected on site. Treatments provide a replicated dose response to 16, 32 and 64 kg N ha^–1 y^–1 adjusted for ambient deposition (8 kg N ha^–1 y^–1). The 16 and 64 kg N ha^–1 y^–1 are duplicated with a P+K supplement. Baseline soil chemistry and foliar nutrient status was established for all 44 plots for Calluna vulgaris, Sphagnum capillifolium, Hypnum jutlandicum and Cladonia portentosa.     

On Sand and Duststorms and Associated Significant Dustfall Observed in Chongju-Chongwon,Korea during 1997–2000

Monitoring of the occurrence of sandstorms and dustfallphenomena from 1997 to 2000 was carried out. We refer tosandstorms, duststorms and blowing sand as the phenomenaoccurring in the source region, while significant dustfall is thephenomenon that occur in the sink area. It was noted that while the sandstorms in deserts and loess in NW-N China and Mongolia occurred any time during the year while severe sandstorms occurred frequently from March to May after the springthaw. The wind erosion in the source region usually occurred withwind speeds greater than 8 ms^-1. However, severe sandstorm phenomenon occurred with wind greater than 15 ms^-1 for at least 3 hr or more. In the source regions, sandstorms occurred over60–120 days per year. In Mongolia, the observation of thenumber of sandstorm days decreased due to the increase in rainy days.When a dust cloud from a desert reached the sink region,significant dustfall in the Korean Peninsula occurred due tothe lack of strong winds. We defined the episode ofsignificant dustfall (SD) with the following values: TSP250, PM₁₀ 190 g m^-3 and visibility 6.5 km or less. In Korea, 8–12 episodes of SD occurred per yearwith 12 to 22 SD days. The maximum concentrations of TSP recorded were 989–1396 g m^-3 with PM₁₀ values of 861–996 g m^-3 and with the lowestvisibility of 1.4–1.6 km.     

Pools and Fluxes of Cations,Anions and Doc in Two Forest Soils Treated With Lime and Ash

The effect of liming and ash treatment on pools, fluxes and concentrations of major solutes was investigated at two forestedsites (Norway spruce) in S. Sweden. One site was treated 15 yrprior to sampling (Hasslöv-Hs; dolomite: 3.45 and 8.75 t ha^-1) and the other 4 yr before (Horröd-Hd; dolomite: 3.25 t ha^-1; wood ash: 4.28 t ha^-1). Effects of limingwere most pronounced in the O horizon solutions where higher pH,elevated Ca (120–700 M) and Mg (50–600 M) were observed as compared to control plots. The impact on the mineralsoil was more moderate. Soil solution concentrations were combined with modelled hydrological flow to calculate mass flows,which largely followed the trends of the solution composition. Liming also resulted in large increases of both exchangeable Caand Mg as well as effective cation exchange capacity (CEC_E;2–5 times the controls). The base saturation (BS%) was raised to 60–100% in the O horizon while in the mineral soil elevated values were only seen at the Hs site (20–60%; down to 10–15 cm depth for 8.75 t ha^-1). Ash treatment did notaffect either the soil solution nor the exchangeable pool to thesame extent as lime. In general, the impact at the Hd site was less pronounced especially in the mineral soil, which might be due to shorter treatment time (4 vs. 15 yr) and also differentthickness of the O horizon. Budget calculations for Ca and Mg originating from the lime showed that a major part of the Ca (40–100%) was retained in the top 30 cm of the soil, of which30–95% was present in the O horizon. The mobility of Mg wasgreater and it was estimated that a significant part had been leached from the profile (30 and 50 cm depth) after 15 yr. Increased mass flows of NO₃ ^- due to nitrification resulting from liming at the Hs site were calculated in the range120–350 mmol m^-2 yr^-1 (or 1.2–3.5 kmol ha^-1 yr^-1). There was significant leaching of Al (25–60 mmol m^-2 yr^-1), of which about 70% was inorganic, in thelower B horizon at both sites with no influence of liming.     

Characterization and enzymatic degradation of a cross-linked bacterial polyester

The bacterial polyester, poly(-hydroxybutyrate-co--hydroxyvalerate) (PHB/V), was cross-linked with 1, 5, 7, 10, 20, and 30 wt% benzoyl peroxide by thermal decomposition reactions. Solvent extractions were carried out to determine the cross-linked fractions of the films. The sol/gel data were used to estimate cross-link densities. Films of PHB/V cross-linked with 10% benzoyl peroxide were placed in contact with purified depolymerase A secreted byP. lemoignei. These samples exhibited weight loss rates which were half that of un-cross-linked PHB/V, but the network was degraded completely by the enzyme. The results of this study suggest that anendo-type enzymatic degradation may occur, in addition to theexo-type activity, which is normally presumed to occur with theP. lemoignei depolymerase system.     

Landfill mining and waste characterization: a strategy for remediation of contaminated areas

This article describes landfill-mining tests, including excavation, screening, and fraction characterization, carried out in the Msalycke and Gladsax landfills for municipal solid waste (MSW) in Sweden. The excavated waste in these two sites was 17–22 and 23–25 years old, respectively. The main part of Msalycke was unaffected by degradation, and during excavations no substantial amount of biogas was detected. After screening, three size fractions were obtained: <18mm, 18–50mm, and >50mm. Soil amendment and anaerobic digestion with energy extraction are suggested for the first and second fraction, respectively. Incineration with energy recovery is possible with the third fraction after any coarse (inert) material is removed, and construction/demolition waste can easily be recycled provided that it is not contaminated by hazardous material. Excavated waste taken from different depths was also analysed and compared in relation to composition, calorific value, and leachate constituents.     

Comparison of the Chemical Composition of Mineral Particles Collected in Dunhuang,China and those Collected in the Free Troposphere over Japan: Possible Chemical Modification during Long-Range Transport

The Asian continent is recognized as one of the most important sources of mineral (or soil) particles. These particles have a large potential to effect global changes through the biogeochemical cycle of particulates and through radiative balance (IPCC Third Assessment Report, 2001). Therefore, comparison of particle compositions near the source region and those after long-range transport is important in understanding the long-range particle transport phenomenon. Individual aerosolparticles were collected in Dunhuang (40°09N; 94°41E), China. Particles were collected at the campus of the Meteorological Bureau of Dunhuang City (17 August 2001) and near the Mogao Grots, located approximately 30 km from Dunhuang (18 August 2001, 18 October 2001 and 13 January 2002) using a two-stage low-volume impactor. The morphology of individual aerosol particles and their elemental compositions were examined via a scanning electron microscope (Hitachi, S-3000N) equipped with an energy dispersive X-ray (EDX) analyzer (Horiba, EMAX-500). The particles collected at these locations were comprised primarily of minerals, with the exception of sulphateparticles in the submicron range that were contained in thesample collected on 18 October 2001 (likely, ammonium sulphate). The most abundant elements were found to be Si and Al. Approximately 46–77% of the collected particles were Si-richparticles (composed primarily of quartz and aluminosilicate),and 13–41% of the collected particles were Ca-rich particles,such as calcite (CaCO₃), dolomite (CaMg(CO₃)₂),and gypsum (CaSO₄2H₂O). The fractions of Fe-rich, Mg-rich, Ti-rich, K-rich, and Cl-rich were 3–10, 0–7, 0–3, 0–1, and 0–1%, respectively. Similar types of mineral particles were found in the free troposphere over Japan(Trochkine et al., 2002). A number of differences were found to exist between the particles collected in China and thosecollected in Japan, and these differences can be explained bychemical modification of the particles during transport fromChina to Japan.     

Quantifying dry NH3 deposition to an ombrotrophic bog from an automated NH3 field release system

Providing an accurate estimate of the dry component of N deposition to low N background, semi-natural habitats, such as bogs and upland moors dominated by Calluna vulgaris is difficult, but essential to relate nitrogen deposition to effects in these communities. To quantify the effects of NH₃ inputs to moorland vegetation growing on a bog at a field scale, a field release NH₃ fumigation system was established at Whim Moss (Scottish Borders) in 2002. Gaseous NH₃ from a line source was released along of a 60 m transect, when meteorological conditions (wind speed >2.5 m s^–1 and wind direction in the sector 180–215°) were met, thereby providing a profile of decreasing NH₃ concentration with distance from the source. In a complementary study, using a NH₃ flux chamber system, the relationships between NH₃ concentrations and cuticular resistances were quantified for a range of NH₃ concentrations and micrometeorological conditions for moorland vegetation. Cuticular resistances increased with NH₃ concentration from 11 s m^–1 at 3.0 g m^–3 to 30 s m^–1 at 30 g m^–3. The NH₃ concentration data and the concentration-dependent canopy resistance are used to calculate NH₃ deposition taking into account leaf surface wetness. The implications of using an NH₃ concentration-dependent cuticular resistance and the importance for refining critical loads are discussed.     

Plastic shaping of aqueous alumina suspensions with sucrose and maltodextrin additives

Traditional methods for the shape-forming of engineering ceramics entail plastic deformation of powder slurries containing hazardous organic liquids as suspending media. Replacing these organic with aqueous media requires the development of environmentally benign, water-soluble additives which serve as plasticizers and binders. Fundamental studies were performed with aqueous suspensions of colloidal-Al₂O₃ to evaluate the role of sucrose and maltodextrin on viscosity, sedimentation, and filtration characteristics, plastic flow behavior of filter cakes, and sinterability. Maltodextrin systems exhibited superior results, including filtration to high packing densities and clay-like plasticity with minimal cracking.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract W-7405-Eng-82.     

Investigation of Boundary Layer Fine Structure in Arid Regions: Injection of Fine Dust into the Atmosphere

Fine structure of the atmospheric boundary layerin desert regions of Kalmykia and on dried bottom of theAral Sea and its relation to soil particle emission in theatmosphere are discussed. It was found that in a hot seasonin the absence of dust storms convective processes lift updust particles into the atmospheric boundary layer fromsandy landscapes of Kalmykia and Sub-Aral regions. Thisaerosol consists of aggregate particles and contains asignificant amount of long-living aerosol of size less than5 m (including fine-dispersion 0.01–0.1 maerosol). The increasing of fine aerosol concentration wasfound at air temperature above 25 °C, surfacetemperature above 50 °C, and relative humidityless than 40–50%. Some mechanisms influencing the particle emission rates are briefly considered.     

The Impact of Conifer Harvesting on Stream Water Quality: A Case Study in Mid-Wales

A 12-year record of water quality data for runoff from a spruce forested hillslope with podzolic soils shows the impacts of conifer harvesting and replanting in relation to nitrate generation and its influence on surface water acidification. With felling, nitrate increases from a background of 18 Eq/l to about 50 Eq/l after 1 to 2 years and then declines to background levels over the next 1 to 2 years and to lower concentrations thereafter. This change is mirrored by an acidification process as manifest by a change in Gran alkalinity, acid neutralization capacity (ANC) and aluminium concentrations as well as pH. For example, Gran alkalinity and ANC, which start at negative concentrations prior to felling (about –20 and –50 Eq/l, respectively), become more negative (–30 and –100 Eq/l, respectively) at high nitrate concentrations. Correspondingly, pH decreases from about 4.7 to 4.5 and aluminium concentrations increase from about 14 to 16 M. Subsequently, the acidification is reversed as nitrate concentrations decline and after five years post-felling the system has higher pH, Gran alkalinity and ANC together with lower aluminium concentrations than even before the felling took place (the post-felling values are about 4.9, -15 Eq/l, –20 Eq/l and 7 M/l, respectively).Other determinands show clear changes over time. For example, there is a marked increase in sodium and chloride prior to and around the time of felling (200 to 300 and 230 to 400 Eq/l, respectively), with a subsequent decline in concentration to pre-felling and to lower values of around 160 and 170 Eq/l, respectively, thereafter. This change is probably associated with abnormally high inputs of sea-salts from the atmosphere during the first quarter of the year of felling, and dilution thereafter, rather than a direct consequence of the felling activity itself: this change in sea salt loading has had an impact on stream acidity. Dissolved organic carbon and iron also change with concentrations increasing over time (60 to 200 and 1.0 to 1.5 M/l, respectively) and this mirrors a general pattern observed across the Plynlimon catchments irrespective of whether or not there has been felling activity.The implications of the findings are discussed in relations to environmental management and hydrochemical processes.     

On East Asian Sand and Duststorms and Associated Significant Dustfall Observed from January to May 2001

Monitoring of dust pollution at the western shore of Tae-ahn Peninsula (TAP) and in the Chongju area of central Korea was carried out from January to May 2001. It was found that in Koreathere were 9 cases of sand and duststorms (DS) and 16 associatedsignificant dustfall (SD) days. Observed maximum concentrations of DS and SD coming from NW China and Mongolia were in the rangeof 300–920 for TSP, 200–690 for PM₁₀ and 100–170 g m^-3 for PM_2.5.Satellite measurements clearly showed the formation and subsequent movement of DS to the Korean Peninsula and onward to the Korea East Sea, Japan and the Gulf of Alaska. According to satellite image analysis of dust clouds there were abundant coarse particles, measuring in size of 11.0 m. Medium-sizedparticles measuring in the range of 3.5–7.0 were also prevalent,while fine particles of less than 2.0 m were less distinctive in reflectivity. Measured values of PM_2.5 were alsorelatively low with SD events.The measured average pH values of dusty precipitation associatedwith DS were 7.24. Alkaline precipitation can play a `temporary'role in the neutralization of acidified soil until the subsequentevent of acidic rain. The new selection criteria of SD days from PM_2.5 at 85 g m^-3, PM₁₀ 190 g m^-3 and TSP 250 g m^-3 are recommended on dust pollution occurring from the invasion of a DS elsewhere.     

Synthesis of cellulose-fatty acid esters for use as biodegradable plastics

Long-chain fatty acid carbohydrate esters (FACE) were synthesized by the acid chloride-pyridine reaction to different degrees of substitution (DS). The hydrolyzed soybean oil was used as the source of unsaturated fatty acids. High molecular weight FACE polymers are insoluble in common solvents, such as benzene, toluene, THF, etc., and are highly water resistant. However, FACE polymers of hydrolyzed cellulose (MW 180 kD) are soluble/swellable in toluene and can be cast into tough, flexible films. FACE polymer properties of tensile strength and clasticity vary with degree of substitution and polymer size.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

One-Pot Reaction of Waste PET to Flame Retardant Polyurethane Foam,via Deep Eutectic Solvents-Based Conversion Technology

Depolymerization of polyethylene terephthalate (PET) is a promising technology for producing recycled monomers. Using a deep eutectic solvent (DES)-based catalyst, the PET glycolysis process produces bis-(2-hydroxyethylene terephthalate) (BHET). This recycled monomer reacts with isocyanate and forms polyurethane foam (PUF). The DES-based one-pot reaction is advantageous because it is a low-energy process that requires relatively lower temperatures and reduced reaction times. In this study, choline chloride/urea, zinc chloride/urea, and zinc acetate/urea based DESs were adopted as DES catalysts for glycolysis. Subsequently, the conversion of PET, BHET yield, and OH values were evaluated. Both filtered and unfiltered reaction mixtures were used as polyols for PUF polymerization after characterization of the acid and hydroxyl values of the polyols, as well as the NCO (–N=C=O) value of isocyanate. In the case of unfiltered reaction mixtures, PUF was obtained via a one-pot reaction, which exhibited higher thermal stability than PUF made from the filtered polyols. This outcome indicated that oligomeric BHET containing many aromatic moieties in unfiltered polyols contributes to the thermal stability of PUF. This environmentally friendly and relatively simple process is an economical approach for upcycling waste PET.