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.     

Sulfur Metabolism in Polluted Sphagnum Peat Bogs: A Combined 34S–35S–210Pb Study

The size and isotopic behavior of sulfur pools in²¹⁰Pb-dated peat cores were investigated to obtain aninsight into retention mechanisms of pollutant S in twomountain-top peatlands of the Northern Czech Republic, CentralEurope. The bogs were situated 40 km apart in an area whichbetween the years 1985 and 1995 received as much as 130 kg Sha^-1 yr^-1 from the atmosphere. Vertical peataccretion was faster at Pod Jelení horou (JH) than atVelký moál (VM). Organic carbon-bonded S was themost abundant sulfur pool, constituting 77 and 65 wt. % at JHand VM, respectively. At JH both the S concentration maximumand the highest annual S deposition rate were displaceddownward by more than 20 years (from 1987 to the 1960s)indicating that the buried S is vertically mobile. At VM the Sconcentration was the highest in the topmost 2-cm section eventhough atmospheric S deposition peaked in 1987. Differentmechanisms of S isotope redistribution prevailed in thetopmost peat layers at JH, where a negative ³⁴Sshift occurred, and at VM, where a positive ³⁴Sshift occurred. Bacterial sulfate reduction was responsiblefor the negative ³⁴S shift at JH. One possibleexplanation of the positive ³⁴S shift at VM isrelease of ³²S-enriched products of mineralization duringpeat diagenesis. There was a strong positive correlationbetween the abundance of total and pyrite S along the profiles.The presence of pyrite S at VM (526 ± 60 ppm) suggestedthat even at VM bacterial sulfate reduction occurred. Ananaerobic incubation of JH peat indicated sulfate reductionrate of 600 nmol g^-1 day^-1. The turnover times forinorganic S pools were shorter than for the organic S pools.Cumulative S contents in the Czech peat bogs were found to besignificantly lower than in similar sites in the NortheasternU.S., even though the atmospheric S inputs were more thanthree times higher at the Czech sites. Possible causes of suchdiscrepancy are discussed.     

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.     

The Application of Stable Isotopes for Assessing the Hydrological, Sulfur, and Iron Balances of Acidic Mining Lake ML 111 (Lusatia, Germany) as a Basis for Biotechnological Remediation

Stable isotope (¹⁸O–H₂O, ²H–H₂O ³⁴S–SO₄ ^2-) andhydrochemical data (SO₄ ^2-, Fe-concentrations) have beenused to estimate the annual groundwater inflow and outflow of mining lake ML 111 and to calculate the total amount of dissolvedsulfate and iron that is carried into the lake by groundwater. The hydrological balance suggests an annual groundwater inflow of 23 700 m³ and an annual groundwater outflow of 15 700 m³. The calculation of the sulfur and iron balances yielded an annual sulfate input of 37 800 kg and an annual iron input of 7000 kg with the groundwater inflow. Furthermore it was shown that significant fluxes of these elements go into the lake sediments which results in continuous release of acidity in the lake water.     

Synthesis and environmental degradation of polyesters based on poly (ε-caprolactone)

Poly (-caprolactone) (PCL), poly (-valerolactone) (PVL), poly (-caprolactone-co--valerolactone) [P(CL-co-VL)], and poly (-caprolactone-co-ethylene oxide-co--caprolactone) (PCL-PEO-PCL) were synthesized by ring-opening and diol-initiated polymerization of -caprolactone and -valerolactone. The degradation of the samples by chemical hydrolysis and in a soil burial test was evaluated. It was found that PCL, PVL, and P(CL-co-VL) degrade mainly enzymatically. The rate of degradation depends on their molecular weight, chemical structure, composition, and morphology. PCL-PEO-PCL block copolymers exhibit a repelling effect to the microorganisms in the soil, which depends on the molecular weight and relative amount of PEO block in the copolymer.     

The Effect of Nitrogen Enrichment on the Carbon Sink in Coniferous Forests: Uncertainty and Sensitivity Analyses of Three Ecosystem Models

Estimates of the global carbon sink induced by nitrogen enrichment range vary widely, from nearly zero to 2.3 Gt C year^-1. It is necessary to reduce this uncertainty if we are to make accurate predictions of the future magnitude of the terrestrial carbon sink. Here, we present a Monte Carlo approach to uncertainty and sensitivity analysis of three ecosystem models, Century,BGCand Hybrid. These models were applied to a coniferous forest ecosystem in Sweden. The best estimate of the change in total carbon content of the ecosystem with the cumulative change in nitrogen deposition over 100 years, C_total/N_deposition was 20.1 kg C (kg N)^-1 using the pooled mean, with a pooled standard deviation of 13.8 kg C (kg N)^-1. Variability in parameters accounted for 92% of the total uncertainty in C_total/N_deposition, and only 8% was attributable to differences between models. The most sensitive parameters were those which controlled the allocation of assimilate between leaves, roots and stem. In particular, an increase in allocation to fine roots led to a large reduction in C_total/N_deposition in all models, because the fine roots have a very high turnover rate, and extra carbon allocated there is soon lost through mortality and decomposition.     

Air Pollution Effects on Forest Trees in Balikesir,Turkey

Air pollution has become an actual problem in Balikesir because of rapid urbanisation and increasing of the polluting sources. Air pollutionproblems occur under the unfavorable meteorological conditions which increase in frequency of occurrence in winter due to use of low quality lignite coals for heating. The `Protection of Air Quality' in Turkey dated 1986 is based on the human health criteria. But the critical limit values are lethal for the forest trees as far as SO₂ is concerned. The field observations showed that leaves of the trees have yellow spots indicating acid burns in Balikesir. This study aims at determining the relationships between the SO₂ concentrationsin the air under selected climatic conditions, and the effects of air pollution on forest trees in Balikesir. Samples of leaves were collected from the City Parks in Balikesir, Deirmenboaz forested area located 10 km far fromBalikesiron the Balikesir-Bursa highway, and from the forestation areas near the Balikesir-Edremit highway. Sulfur contents of the leaves were very high especially in the city (2650–5300 g m^-3).Samples from other areas had values lower than this range but above the usual values (850–3612 g m^-3). The diameter increments of the trees were found to be lower and these results clearly showed the adverse impacts. Negative correlations were found between these sulfur concentrations and the daily mean temperatures and wind speeds. Positive correlation was seen between these concentrations and pressures, humidities. Emission sources must be controlled in order to safeguard the forests which protects the soil, facilitate water production, assimilate carbon dioxide in air and produce oxygen. It must be considered that the problems are not only regional but have a global identity.     

A New Approach for the Flocculation Mechanism of Chitosan

A peak III/I ratio (_peak) in pyrene-fluorescence spectrum was used to measure the polarity of microenvironment of chitosan adsorbing pyrene molecules. The authors detected the pyrene-fluorescence spectrum of chitosan with different degrees of deacetylation (DD) and determined the relationship between the flocculation of bentonite colloid and the _peak of chitosan with a different molecular weight (MW) and DD. It can be concluded that MW rather than DD plays a key role in the flocculation and that bond bridging rather than charge neutralization dominates the flocculation with chitosan from a microenvironmental structure of view.     

Winter and Spring Thaw Measurements of N2O,NO and NOx Fluxes using a Micrometeorological Method

The impact of nitrogen fertilizers on gaseous emissions duringwinter and spring-thaw is not well understood and was the objective of this research. Using a micrometeorological method,N₂O, NO and NO_x fluxes from ryegrass were measured from November 1997 to March 1998. Three different mineralfertilizers were applied in November: urea (U), slow-release urea(SRU) and ammonium nitrate (AN). N₂O emissions during the winter were small, increasing significantly in March. Total losses of N₂O-N were significantly higher from SRU and U plots, with winter N₂O emissions accounting for 50% of annual losses. Nitric oxide fluxes from all plots weresmall during the measurement period (<0.9 ng N m^-2 s^-1). The NO fluxes from U and AN fertilized plots were significantly higher than from SRU and control plots. NO₂ fluxes were always negative (–6 ng N m^-2 s^-1)indicating deposition, but decreased to –2 ng N m^-2s^-1 when snow was present on the soil surface. Our resultsindicate that the form of inorganic N applied has an effect on NO+ N₂O emissions but not on NO₂ fluxes.Sponsored by CAPES – Brasília, Brazil     

Ring-Opening Polymerization of Cyclic Esters onto Liquefied Biomass

Ring-opening polymerization of cyclic esters (-caprolactone, -valerolactone, and l-lactide) onto liquefied biomass (LB) was conducted to obtain the polyester-type polyol and to regulate the characteristics of LB. IR and ¹H-NMR spectra of the obtained polyol showed that the polymerization was successfully conducted in the presence of acid catalyst, which is used in liquefaction. The molecular weight (M_w), hydroxyl value, and viscosity were controllable by changing the reaction conditions. Polyester-type polyurethane foams with a wide range of properties were prepared from the obtained polyol with the appropriate combinations of foaming agents.     

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.     

Soil Respiration in Relation to Small-Scale Patterns of Lead and Mercury in Mor Layers of Southern Swedish Forest Sites

Pollution-related lead (Pb) andmercury (Hg) in mor layers of Southern Swedenmight have effects on soil biology, although inthe literature effect concentrations have beenidentified at much higher levels. Considerablesmall-scale spatial variability in heavy metalcontents and microbial respiration in mor layersof forest sites was used to calculatecorrelations that could reveal toxic effects.Negative correlations were always strongest atsites with high loads of Pb or Hg, which was considered to indicate metal toxicity. The highload sites were found in Southwestern Sweden,locally at a motorway and at a chlorine-alkalifactory. Other factors of possible influence,such as other pollutants, age of organic materialor climatic differences, would affect high andlow load sites alike. Negative correlations withrespiration were found for Pb at sites with 74 g g^-1 of mean Pb content in O_f-layer and for Hg at 0.25 g g^-1.     

Catalytic decomposition of hydrocarbon into hydrogen and carbon in a spouted-bed reactor as the second-stage reactor of a plastic recycling process

A two-stage process for the chemical recycling of plastics is proposed. In this process, which consists of two reactors, plastics are converted into hydrogen and carbon. In the first reactor, plastic chips are thermally decomposed into hydrocarbons. In the second reactor, the hydrocarbons formed in the first reactor are catalytically decomposed into carbon and hydrogen. In this study, in order to obtain basic data for the second reactor, propene was catalytically decomposed in a laboratory-scale spouted-bed reactor (600mm high, 21.6mm internal diameter, made of SUS304). The effect of the type of spouting medium used on the decomposition behavior of propene was investigated using four types of spouting medium (nickel-plated -alumina, palladium-plated -alumina, nickel-impregnated -alumina, and -alumina). The nickel-impregnated -alumina gave the best propene conversion and hydrogen yield.     

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 for N deposition. 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 δ¹⁵N, 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 δ¹⁵N 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 δ¹⁵N and nitrate reductase data suggest uptake and assimilation of N through the foliage. We conclude that for this lowland deciduous woodland, tissue, xylem and surface measurements of nitrate are unreliable biomarkers for N deposition whereas δ¹⁵N, 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.     

Gas and Aerosol Loadings at Holme Moss 1996–1998 Measurements and Analysis Using Back-Trajectory Clustering

A continuous two-year atmospheric datasetcomprising gas and aerosol loadings from amountain site in northern England (Holme Moss,W1°5130 N53°320) is presented. The data are analysed with respect to three-dayback-trajectories that are grouped according to aclustering technique that allows speed, directionand curvature of the airmass track to beconsidered. The technique is successful inseparating the data into chemically distinctsubsets. Up to 29% of the variance in the datais explained by back-trajectory clusters. Slow trajectories are associated with highloadings especially for the oxides of nitrogen,which may imply a local source for much of thesuspended pollutant. The data suggest thatproduction of nitrate and sulphate is limited byoxidant availability at least in the winter. Itmay be possible to optimise the analytical powerof the technique by increasing the importance ofrecent airmass track in determining clusterallocation. This applies especially to the totalsulphur loading.     

The Role Played by Acetyl Group Distribution Patterns in Substituted Starch Toward Enzymatic De-acetylation and Chain Fragmentation

The nature and distribution of the acetylated groups were evaluated by ¹³C-NMR and ¹H-NMR. The starch substrate with a DS of 1.5 comprises only two patterns: -(14)-d-glucopyranose and 2,3,6-tri-O-acetyl--(14)-d-glucopyranose. The starch with a DS of 3.0 also comprises two patterns: 2,3,4,6-tetra-O-acetyl--(14)-d-glucopyranose and 2,3,6-tri-O-acetyl--(14)-d-glucopyranose; whereas starch (DS = 1.9) contains 4 patterns: 2,3,6-tri-O-acetyl--(14)-d-glucopyranose, 2,3,4,6-tetra-O-acetyl--(14)-d-glucopyranose terminal, 2,6-di-O-acetyl--(14)-d-glucopyranose, and 3,6-di-O-acetyl--(14)-d-glucopyranose. Using esterase from Viscozyme, it has been possible to hydrolyze up to 7% of the DS 3.0 starch. An -amylase (Fungamyl 800) was then added to these acetylesterases. With a 2.4 FAU/mL fraction of -amylase and 2.4 U/mL from the Viscozyme's acetylesterase, 28% of the acetylated end groups were hydrolyzed for the starch substrates with DS 3.0. Moreover, a synergic action between -amylase and acetylesterase was noticed, allowing fragmentation of 32% for DS 1.5, 30% for DS 1.9, and 11% for DS 3.0.     

The degradation of gel-spun poly(β-hydroxybutyrate) “wool”

The apparent biodegradability and biocompatibility of the microbially produced polyester, poly(-hydroxybutyrate) (PHB), has been the focus of much research by a number of authors with regard to its potential for use in packaging and medical implantation devices. PHB has recently been produced by gel-spinning into a novel form, with one possible application being as a wound scaffolding device, designed to support and protect a wound against further damage while promoting healing by encouraging cellular growth on and within the device from the wound surface. This new nonwoven form combines a large volume with a low mass, has an appearance similar to that of cotton wool, and has been called wool because of this similarity. The hydrolytic degradation of this wool was investigated in an accelerated model of pH 10.6 and temperature 70°C. It was determined that the PHB wool gradually collapsed during degradation. The surface area-to-volume ratio was concluded to be a primary influencing factor. Degradation was characterized by a reduction in the glass transition temperatures and melting points and a fusion enthalpy peak of maximum crystallinity, (88%), which coincided with the point of matrix collapse.     

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.     

Mechanical Properties and Lipase-Catalyzed Biodegradation of α-Methyl, ε-Caprolactone/ ε-Caprolactone Copolymers Obtained by Chemical Modification of Poly(ε-caprolactone)

Novel (-caprolactone)-based copolymers of different compositions were synthesized by allowing methyl iodide to react with the polycarbanion that resulted from the action of lithium diisopropylamide on poly(-caprolactone) in THF at –70°C under argon atmosphere. The copolymers were characterized by various techniques, namely ¹H nuclear magnetic resonance, size exclusion chromatography, differential scanning calorimetry, x-ray diffraction and viscoelasticimetry. They were submitted to hydrolytic and lipase-catalyzed enzymatic degradation in comparison with genuine PCL. The Young modulus depended on the degree of methylation. In contrast, loss angle and glass transition temperature did not depend on this parameter. It is shown that the lipase-catalyzed degradation of methylated PCL is much slower than in the case of genuine PCL.     

Nature of Atmospheric Aerosols over the Desert Areas in the Asian Continent: Chemical State and Number Concentration of Particles Measured at Dunhuang,China

Measurements of aerosol were made in August and October 2001, and January 2002, at Dunhuang, China (40°00N, 94°30E), to understand the nature of atmosphericparticles over the desert areas in the Asian continent. Balloon-borne measurements with an optical particle counter suggested that particle size and concentration had a noticeable peak in size range of super micron in not only the boundary mixing layer but also the free troposphere. Thickness of the boundary mixing layer, from distributions of particle concentration, was about 4 km in summer (17 August 2001), about2.5 km in fall (17 October 2001), and about 3 km in winter (11 January 2002), which suggest active mixing of particles near the boundary in summer. Number-size distribution of particleshowed a noticeable peak in the super micron particles size range inthe mixing boundary layer: 0.4–2 particles cm^-3 at diameter>1.2 m in summer, 0.05–4 particles cm^-3 at diameter >1.2 m in fall, and 0.1–5 particles cm^-3 at diameter>1.2 m in winter. In winter strong inversion of atmospherictemperature was found in the height range from the boundary to about 3 km and vertical distribution of particle concentration well corresponded with the temperature distribution. Chemical elements of individual aerosols, which were collectedin the boundary layer atmosphere at Dunhuang (18 October 2001) were analyzed with an electron microscope equipped with EDX. Thosesingle particle analysis suggested that most of the particles with supermicron size were soil particles, and those particles had littlesulfate on its surface. This is a very important different point,comparing with the chemical state of soil particles, which weretransported from the desert area of China to Japan, and showed frequentlythe existence of sulfate on the particle surface. Therefore, it isstrongly suggested that dust particles can be chemically modifiedduring their long-range transport from desert areas to Japan.