Humidity- and Age-Tolerant Starch-Based Sponge for Loose-Fill Packaging

Loose-fill packaging sponges were extruded from mixtures of 54–62% hydroxypropylated (HP 5%) amylomaize V (50% amylose) and wheat starches, 17–24% synthetic polymer, 13% water, 7% blowing agent(s), and 0.5% nucleating agent. One product made from 28% HP wheat starch, 28% HP amylomaize V starch, 12% ethylene vinyl alcohol (EVOH) copolymer, 8% polystyrene (PS), and 3% polystyrene maleic anhydride (PSMA) copolymer, plus the other raw materials, had a compressibility and resilience that matched those of expanded polystyrene (EPS), although its bulk density was four times higher. The starchy sponge showed 16% shrinkage in volume at 90% relative humidity and was 2% soluble in excess water, both at 25°C. After aging for 18 months near 25°C, the HP starchy sponge gave only a trace of fines in a simulated shipping test, compared to 20% fines from a biodegradable, starch-based, loose-fill sponge of commerce.     

Biodegradable Corn Starch Loose-Fill. II. The Effect of Storage at Different Relative Humidities on the Physical Properties of Loose-Fill

The physical properties of corn starch loose-fill were examined at various relative humidities (r.h.). After 48 h of storage at both 25 and 50% r.h., only a slight change in the dimension and physical properties of the corn starch loose-fill was apparent. A wet environment (75% r.h. for 48 h), however, caused significant shrinkage and the loss of physical properties. The tensile properties, particularly tensile modulus, sharply increased, while the resilience gradually decreased with storage time. Amorphous X-ray diffraction patterns of corn starch loose-fills were transformed into crystalline patterns due to aging at 75% r.h. after 48 h. These changes were attributed to the structural relaxation, which was accelerated by moisture gain. The T _g of corn starch loose-fill decreased with increasing the moisture content in expanded starch. Our proposed model based on Avrami equation was able to describe the time-dependent recrystallization of corn starch by modifying the time-dependent tensile modulus. The growth parameter (n) and time constant (k) for the recrystallization process of corn starch loose-fill were about 3.2 and 8.87 × 10^–18 s^–1, respectively. If the growth parameter of 3.2 is considered, spherulitic growth of crystallization occurred in the corn starch loose-fill in the wet environment.     

Measurement of the biodegradation of starch-based materials by enzymatic methods and composting

The aim of this study was to evaluate the suitability of in vitro enzymatic methods for assaying the biodegradability of new starch-based biopolymers. The materials studied included commercial starch-based materials and thermoplastic starch films prepared by extrusion from glycerol and native potato starch, native barley starch, or crosslinked amylomaize starch. Enzymatic hydrolysis was performed using excessBacillus licheniformis -amylase andAspergillus niger glucoamylase at 37°C and 80°C. The degree of degradation was determined by measuring the dissolved carbohydrates and the weight loss of the samples. Biodegradation was also determined by incubating the samples in a compost environment and measuring the weight loss after composting. The results indicated that the enzymatic method is a rapid means of obtaining preliminary information about the biodegradability of starch-based materials. Other methods are needed to investigate more accurately the extent of biodegradability, especially in the case of complex materials in which starch is blended with other polymers.     

Biodegradability: An assessment of commercial polymers according to the Canadian method for anaerobic conditions

The degradation of several biodegradable polymers was measured as a result of exposure to an anaerobic medium. The polymers investigated included materials based upon polylactic acid, polylactone, and poly(hydroxy butyrate/valerate) as well as those incorporating starch-based materials. The degradation was monitored by methane and carbon dioxide evolution. In addition, the physical and chemical changes were noted as a result of exposure. These measurements included changes in mass, dimension, and molecular weight. FTIR, UV-vis, proton, and¹³C NMR spectra were also recorded prior to and after exposure. The results clearly indicated that several biological and chemical degradation processes were occurring with the biodegradable polymers studied.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Issued as NRCC No. 37549.     

The Control of SO2 Dry Deposition on to Natural Surfaces by NH3 and its Effects on Regional Deposition

Two years of continuous measurements of SO₂deposition fluxes to moorland vegetation are reported. The mean flux of 2.8 ng SO₂ m^-2 s^-1 is regulated predominantly by surface resistance (r _c) which, even for wet surfaces, was seldom smaller than 100 s m^-1. The control of surface resistance is shown to be regulated by the ratio of NH₃SO₂ concentrations with an excess of NH₃ generating the small surface resistances for SO₂. A dynamic surface chemistry model is used to simulate the effects of NH₃ on SO₂ deposition flux and is able to capture responses to short-term changes in ambient concentrations of SO₂, NH₃ and meteorological conditions. The coupling between surface resistance and NH₃/SO₂ concentration ratios shows that the deposition velocity for SO₂ is regulated by the regional pollution climate. Recent long-term SO₂ flux measurements in a transect over Europe demonstrate the close link between NH₃/SO₂ concentrations and rc (SO₂). The deposition velocity for SO₂ is predicted to have increased with time since the 1970s and imply a 40% increase in v _d at a site at which the annual mean ambient SO₂ concentrations declined from 47 to 3 g m^-3 between 1973 and 1998.     

Assessment of Bacterial Degradation of Aromatic Hydrocarbons in the Environment by Analysis of Stable Carbon Isotope Fractionation

¹³C/¹²C stable carbon isotope fractionation was used to assess biodegradation in contaminated aquifers with toluene as a model compound. Different strains of anaerobic bacteria (Thauera aromatica, Geobacter metallireducens, and the sulfate-reducing strain TRM1) showed consistent ¹³C/¹²C carbon isotope fractionation with fractionation factors between C = 1.0017 and 1.0018. In contrast, three cultures of aerobic organisms, using different mono- and dioxygenase enzyme systems to initiate toluene degradation, showed variable isotope fractionation factors of C = 1.0027 (Pseudomonasputida strain mt-2), C = 1.0011 (Ralstonia picketii), andC = 1.0004 (Pseudomonas putida strain F1). The great variability of isotope fractionation between different aerobic bacterial strains suggests that interpretation of isotope data in oxic habitats can only be qualitative. A soil column was run as a model system for contaminated aquifers with toluene as the carbon source and sulfate as the electron acceptor and samples were taken at different ports along the column. Microbial toluene degradation was calculated based on the ¹³C/¹²C isotope fractionation factors of the batch culture experiments together with the observed ¹³C/¹²C isotope shifts of the residual toluene fractions. The calculated percentage of biodegradation, B, correlated well with the decreasing toluene concentrations at the sampling ports and indicated the increasing extent of biodegradation along the column. The theoretical toluene concentrations as calculated based on the isotope values matched the measured concentrations at the different sampling ports indicating that the Rayleigh equation can be used to calculate biodegradation in quasi closed systems based on measured isotope shifts. A similar attempt was performed to assess toluene degradation in a contaminated, anoxic aquifer. A transect of groundwater wells was monitored along the main direction of the groundwater flow and revealed decreasing concentrations accompanied with an increase in the ¹³C/¹²C stable carbon isotope ratio of the residual toluene. Calculation of the extent of biodegradation based on the isotope values and laboratory derived isotope fractionation factors showed that the residual toluene was degraded to more than 99% by microbial activity. Calculation of the theoretical residual toluene concentrations based on the measured isotope values described the strongly decreasing concentrations along the plume. Other aromatic hydrocarbons like benzene and naphthalene which were analysed in the same course also showed decreasing concentrations along the groundwater flow path accompanied by increasing ¹³C values indicating biodegradation.     

Water vapor permeability of biodegradable polymers

The water vapor transmission rates (WVTR) of several biodegradable polymers were evaluated to determine their suitability as water-resistant coatings and to understand WVTR better in terms of polymer structure. Values of WVTR at 25‡C ranged from 13 to 2900 g/m² /day and increased in the order PHBV PLA (cryst.) PLA (amorph.) PCL Bionolle BAK 1095 CAP CA. Values of WVTR were positively correlated with higher polymer solubility parameters, lower crystallinities, and higher free volumes. Although the WVTR of biodegradable polymers are much higher than those of good barrier materials such as low-density polyethylene, they are sufficient for short-term (hours to days) protection of polysaccharide-based materials against water. Product names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.     

Biodegradable corn starch loose- fill. I. The effect of the extrusion temperature on the physical properties of loose-fill

Extrusion with an intermeshing corotating twin-screw extruder with a limited amount of water caused structural changes in corn starch. The structural changes resulted in a transformation-from a semicrystalline to an amorphous state and the development of orientation of molecular chains in the amorphous region during extrusion. These structural changes, in turn, caused an increase in theT _g, tensile strength, and resilience of the extruded corn starch. Our experimental results showed that the tensile properties and resilience of the expanded corn starch extruded at 240‡C were the best: tensile strength, 1.7 kPa; tensile modulus, 40.4 kPa; and resilience, 57.2%. Extrusion produced an expanded corn starch suitable for protective loose-fill.     

Tree Leaf Biomarkers for Atmospheric Nitrogen Deposition

The aim of this paper was to investigate the effects of nitrogen (N) deposition on tree N cycling and identify potential biomarkers forNdeposition. Between April and October 2002 extensive fieldwork was undertaken at Mardley Heath in Hertfordshire. This woodland, located adjacent to the A1(M) motorway, is exposed to high levels of atmospheric nitrogen oxides from the traffic. Measurements of ¹⁵N, in vivo nitrate reductase (NR) activity, tissue, xylem and surface nitrate concentrations as well as N concentration and growth were made along a 700-m transect at 90° to the motorway. The ¹⁵N data show that oxidised N from the road traffic is taken up by nearby trees and is incorporated into plant tissues. Our measurements of NR activities suggest elevated rates close to the motorway. However, xylem sap, leaf tissue and leaf surface nitrate concentrations showed no differences between the roadside location and the most distant sampling point from the motorway. Taken together the ¹⁵N and nitrate reductase data suggest uptake and assimilation of N through the foliage.We conclude that for this lowland deciduouswoodland, tissue, xylem and surface measurements of nitrate are unreliable biomarkers for N deposition whereas ¹⁵N, growth measurements and integrated seasonal NR might be useful. The results also point to the benefit of roadside tree planting to screen pollution from motor vehicles.     

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.     

Study on the conversion of waste plastics/petroleum resid mixtures to transportation fuels

Catalytic coprocessing of model and waste plastics with light Arabian crude oil residue was investigated using NiMo/Al₂O₃, ZSM-5, FCC, and hydrocracking catalysts. Reaction systems that were studied included low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP). A series of single (plastic/catalyst) and binary (plastic/resid/catalyst) reactions were carried out in a 25-cm³ micro autoclave reactor under different conditions of weight and type of catalyst, duration, pressure, and temperature. The optimum conditions selected for our work were: 1% catalyst by weight of total feedstock weight, 60min reaction time, 8.3Mpa of H₂, and 430°C. The product distribution for the binary system using plastic and petroleum residue provided some encouraging results. High yields of liquid fuels in the boiling range of 100°–480°C and gases were obtained along with a small amount of heavy oils and insoluble material such as gums and coke. In general, this study helps to demonstrate the technical feasibility of upgrading both waste plastics and petroleum resid, as well as an alternative approach to feedstock recycling.     

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.     

Metabolic and Environmental Control on Methane Emission from Soils: Mechanistic Studies of Mesotrophic Fen in West Siberia

The biological mechanisms regulating methane emission fromnatural wetlands are the focus of this article. A novel techniqueprovides estimates of the distribution of CH₄ sources withinan undisturbed soil profile by recording the transient gasdynamics after soil enclosure by deep (50 cm) chamber. Thecombined use of conventional surface and soil chambers across a200-m fen transect allowed us to relate the observed methaneemission to its instant generation and uptake. Surprisingly, themethane generation was relatively constant (9–12 mg CH₄-C hr^-1 m^-2) and highly variable net emission (0.2–20 mg CH₄-C hr^-1 m^-2) was closely correlated (r = –0.809)with methane uptake. In laboratory incubations, CH₄ uptakefollowed Michaelis-Menten kinetics. Added chloride and nitrateirrespective of the cation's nature suppressed uptake as a strongnoncompetitive inhibitors (K _i 0.5 mM). The methaneformation turned out to be unstable and under anaerobicincubation, the formation of CH₄, CO₂ andH₂displayed sustained weekly oscillations. We conclude that effectsof environmental factors alone are not sufficient topredict the variation in emission, which depends also on metabolic control of respective soil organisms. The multitude ofsuch controls is dependent on diversity of respective soilorganisms and could be grouped into a limited number ofcategories considerably simplifying large-scale simulations.     

Remediation of Persistent Organic Pollutants Using a Novel Two-Phase Soil Washing Biosorption Process

A two-phase soil washing biosorption process was developed for the remediation of p,p-DDT-contaminated soil. The process involved desorption of contaminants from soil using dilute primary alcohols (40% 1-propanol) followed by contaminant removal from cosolvent solutions using fungal biosorption. Bench scale remediation studies were preformed to simulate ex situ (recycling experiment) or in situ (soil column study) treatment strategies. Both systems were effective at cleaning the soil to below Australian regulatory p,p-DDT levels. After 50–80 hours of soil washing, over 93% of p,p-DDT was removed from the soil(990 mg kg^-1 to <65 mg kg^-1) using either of these methods.p,p-DDT was removed from the cosolvent phase by sorption onto the fungal biomass. This resulted in only low levels of p,p-DDT remaining in the cosolvent solution(<1.5 mg l^-1). The application of both treatment strategies resulted in the rapid clean up of p,p-DDT-contaminated soil and the potential to recycle cosolvent solutions. The ability to recycle cosolvent solutions provides a mechanism for cost reductions of the remediation strategy.     

Hysteresis in Reversal of Central European Mountain Lakes from Atmospheric Acidification

Extremely high emissions of S and N compounds in Central Europe (both 280 mmol m^-2 yr^-1) declined by 70and 35%, respectively, during the last decade. Decreaseddeposition rates of SO₄ ^-2, NO₃ ^-, and NH₄ ⁺ in the region paralleled emission declines. The reduction in atmospheric inputs of S and N to mountain ecosystemshas resulted in a pronounced reversal of acidification in the Tatra Mountains and Bohemian Forest lakes. Between the 1987–1990and 1997–1999 periods, concentrations of SO₄ ^-2 and NO₃ ^- decreased (average ± standard deviation) by 22±7 and 12±7 mol L^-1, respectively, in theTatra Mountains, and by 19±7 and 15±10 mol L^-1, respectively, in the Bohemian Forest. Their decrease was compensated in part (1) by a decrease in Ca²⁺ + Mg²⁺ (17±7 mol L^-1) and H⁺ (4±6 mol L^-1), and an increase in HCO₃ ^-(10±10 mol L^-1) in the Tatra Mountains lakes, and (2) by a decrease in Al (7±4 mol L^-1), Ca²⁺ + Mg²⁺ (9±6 mol L^-1), and H⁺ (6±5 mol L^-1), in Bohemian Forest lakes. Despite the rapid decline in lake water concentrations of SO₄ ^-2 and NO₃ ^- in response to reduced S and N emissions, their present concentrations in some lakes are higher than predictionsbased on observed concentrations at comparable emission rates during development of acidification. This hysteresis in chemical reversal from acidification has delayed biological recovery of the lakes. The only unequivocal sign of biological recovery hasbeen observed in erné Lake (Bohemian Forest) where a cladoceran species Ceriodaphnia quadrangular has recentlyreached its pre-acidification abundance.     

Correlating the Spatial Distribution of Atmospheric Ammonia with δ15N Values at an Ammonia Release Site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using ¹⁵N values in determining the area of influence around a point NH₃ emission source. ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of ¹⁵N enrichment. Significant linear correlations between ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

Effect of Crystalline and Amorphous Structures on Biodegradability of Poly(Tetramethylene Succinate)

The effect of orientation in the amorphous and crystalline regions on the biodegradability of PTMS [poly(tetramethylene succinate)] was studied using the amorphous orientation function, birefringence, and crystallinity. The crystalline and amorphous intrinsic lateral sonic moduli, E _t,c ⁰ and E _t,am ⁰ , were 2.61 × 10³ and 0.41 × 10³ MPa, respectively. Using the data on birefringence, crystalline and amorphous orientation function (f and f _am), crystallinity, and sonic modulus of the oriented PTMS fibers, the intrinsic birefringence of the crystalline ( _c ⁰ ) and amorphous ( _am ⁰ ) regions were evaluated to be 0.0561 and 0.0634, respectively. The biodegradabilities of oriented PTMS films were reduced as the elongation increased, i.e., the amorphous orientation increased. At low elongation (100 and 150%), however, biodegradabilities remained unchanged when the degradation test was performed in activated sludge, which was attributed to the amorphous orientation occurring even at 100% elongation, though the amorphous orientation direction was perpendicular to the fiber axis.     

Species Composition of Freshwater Invertebrates in Relation to Chemical and Physical Factors in High Mountains in Soutwestern Norway

The composition of benthic invertebrates was investigated in three Norwegian alpine watersheds during the period 1991–1997. The watersheds represented an environmental gradient in chemical factors. The Kvenna watershed was relatively well buffered, Lake Øvre Neådalsvatn was poorly buffered, but receives low inputs of atmospheric pollution while Lake Stavsvatn has low buffering capacity and receives larger inputs of acidifying components. Qualitative samples were taken in the inlet rivers, lake littoral zone, lake outlet and in the outlet rivers of the lakes for analyses of species composition. In Ø. Neådalsvatn the water chemical data showed strong seasonal variations with waters of low ionic content during snowmelt and summer, while increased ion concentrations build up during winter. The time of ice break and/or water temperature rise during the growing season affected the life cycle of Siphlonurus lacustris and Parameletus chelifer. Even small changes in pH or ANC seemed to have a strong effect on Baetis rhodani. In the Kvenna watershed eight very sensitive species were found at sites with pH 6.5, Ca 1.2 mg L^-1 and LAl < 10 eq L^-1. Only two highly sensitive species, B. rhodani and Capnia sp. were recorded when pH was 6, concentration of calcium 0.8 mg L^-1 and low labile aluminium < 10 eq L^-1. None of the highly sensitive species occurred in Stavsvatn, a formerly acidified area, where LAl concentrations ranged between 25–40 eq L^-1. Low ionic content and elevated concentrations of labile aluminium are suggested to exclude sensitive invertebrates in alpine lakes. Synergistic effects of dilute water and harsh climate are assumed to increase sensitivity of invertebrates to acid water. Global warming will result in higher precipitation and more snow in the west Norwegian alpine area. This will shorten the growing season, increase the amount of dilute water and consequently threaten invertebrate species living close to their tolerance limits.     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.