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.     

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.     

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.     

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.     

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.     

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.     

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.     

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with Carbokalk, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H₂S completely. Thus, some H₂S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.     

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.     

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     

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.     

Mercury and Organochlorine Contamination in Brown Trout (Salmo Trutta) and Arctic Charr (Salvelinus Alpinus) from High Mountain Lakes in Europe and the Svalbard Archipelago

High concentration of Hg, less volatile PCB congeners and p,p-DDE in Arctic charr from an arctic lake was mainly causedby biomagnification in the food chain where cannibalism was thedriving force. We suggest that low sediment fluxes of Hg, low net production of methyl mercury, and short food chains excludingpiscivory explain the low levels of Hg in the invertebrate feeding fish population in five European high mountain lakes.Concentrations of less volatile PCB congeners in insectivorous fish populations from the European high mountain lakes were mainly influenced by fish age and atmospheric deposition, indicated by the sediment inventory. Atmospheric deposition influenced by local sources may explain the higher concentrationsof pesticides (p,p-DDT, p,p-DDE and -HCH) observedin fish from the Pyrenees compared to the other sites. Theconcentrations of Hg and organochlorines did not exceedthe guidelines for fish consumption, except for Hg levelsin the oldest fish from the arctic lake.     

Solid State Reactions of Potato Starch with Urea and Biuret

Reaction of granular potato starch with urea and biuret resulted in the formation of products, which were soluble neither in cold nor boiling water. The net reaction was a monosubstitution of the hydrogen atom in one hydroxyl group in each D-glucose unit of starch with the either CO–NH₂ or CO–NH–CO–NH₂ moiety, respectively. Properties of the products, particularly these with urea, depended on the mode of reaction. Reactions were carried out in the microwave oven as well as with convection heating. The products retained the granular form of starch but a vast majority of granules were damaged. -Amylolysis of those materials revealed that their susceptibility to the enzyme increasing in the order: starch-amylolysis with simultaneous insolubility in water make these products suitable as ruminant fodder and, eventually, biodegradable material.     

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.     

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.     

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 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.     

In situ bioremediation of a hydrocarbon polluted site with cyclodextrin as a coadjuvant to increase bioavailability

Bioavailability is one main factor that influences the extent of biodegradation of hydrocarbons. They are very poorly soluble in water and easily adsorbed to clay or humus fractions, so they pass very slowly to the aqueous phase where they are metabolised by microorganisms. Cyclodextrins are natural compounds that form soluble inclusion complexes with hydrophobic molecules and increase degradation rate of hydrocarbons in vitro. In the perspective of an in situ application, we previously checked that -cyclodextrin does not increase eluviation of hydrocarbons through the soil and consequently does not increase the risk of groundwater pollution. The results of an in situ application of -cyclodextrin for bioremediation of a hydrocarbon polluted site are presented. We stated that the combination of bioaugmentation and enhanced bioavailability due to -cyclodextrin was effective for a full degradation.     

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.