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.     

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.     

Adsorption of Pb2+ and Cd2+ on the l-cysteine-functionalized graphene oxide/chitosan/polyvinyl alcohol hydrogel: Kinetic,isotherm, and thermodynamic study

In this study, polyvinyl alcohol-chitosan-cysteine-functionalized graphene oxide (PCCFG) hydrogel was synthesized from l -cysteine-functionalized graphene oxide (CFG), chitosan (CS), and polyvinyl alcohol (PVA). The hydrogel was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy and employed for removing lead ion (Pb²⁺) and cadmium ion (Cd²⁺) from aqueous solution. The effects of initial metal ion concentration, hydrogel dose, pH, time, and temperature were studied. The experimental data were well described by a pseudo-second-order kinetic model and Langmuir isotherm with maximum adsorption capacities of 250 and 192 mg g⁻¹ at 25°C for Pb²⁺ and Cd²⁺, respectively. The adsorption capacity of the PCCFG hydrogel increased with an increase in temperature. The value of ∆G° was negative, which shows the spontaneity of the reaction (electron exchange or ion exchange) between the metal ion and electron-rich atoms (–N, –S, –O). The positive ∆H° shows that the adsorption reaction consumes energy and the positive ∆S° shows the strong affinity of PCCFG toward the Pb²⁺ and Cd²⁺ ions. Pb²⁺ had better affinity and less spontaneity than Cd²⁺. The results show that the coexistence of Pb²⁺, Cd²⁺, and Cu²⁺ in the solution inhibits the adsorption capacity of PCCFG.     

Early Effects of Atmospheric Ammonia Deposition on Calluna Vulgaris (L.) Hull Growing on an Ombrotrophic Peat Bog

This paper reports data from a field study investigating the impacts of elevated ammonia (NH₃) deposition on Calluna vulgaris growing on an ombrotrophic peat bog in S.E. Scotland. Shoot extension, foliar N concentrations, chlorophyll concentration and chlorophyll fluorescence were measured during the second growing season of exposure to a gradient of ammonia concentrations. Results indicate that NH₃ increases growth between 150–200 kg N ha^–1y^–1 cumulative deposition. Foliar N content increased significantly in response to NH₃ cumulative deposition up to 400 kg N ha^–1 y^–1 whereas chlorophyll a content significantly decreased. Measurements of Fv/Fm suggest that although NH₃ exposure altered the growth and reduced chlorophyll a, the efficiency of photosystem II was insensitive to NH₃-N deposition at this stage.     

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.     

Accumulation of pollutant nitrogen in calcareous and acidic grasslands: Evidence from N flux and 15N tracer studies

Semi-natural calcareous and acidic grasslands are known to be sensitive to increased atmospheric N deposition. However, the fate of pollutant N within these systems is unknown. This paper reports on the first studies to determine the fate of added N within a calcareous and an acidic grassland subject to long-term simulated enhanced N deposition. Intact soil/turf cores were removed from field plots treated for six years with enhanced N deposition (ambient +0, +35 and +140 kg N ha^–1 year^–1). Cores were inserted into lysimeters and output fluxes of N were monitored in detail. Complete N budgets—calculated from the N flux data—showed considerable accumulation of N within the treated grasslands, up to 76% and 38% of pollutant N in the calcareous and acidic grasslands respectively. In the second study, the short-term (21 day) fate of pollutant N was determined by tracing ¹⁵N labelled ammonium nitrate (+35 kg N ha^–1 year^–1) though the acidic and calcareous lysimeters into plant, soil and leachate pools. Up to 91% and 59% of ¹⁵N was recovered in soils and vegetation of the calcareous and acidic grasslands respectively, with negligible amounts recovered in soil extractable ammonium and nitrate (<0.3%) and in leachate (<0.02%). This rapid short-term immobilisation of pollutant N supports the long-term accumulation of the element calculated from the N flux study.     

Melt Processing of a New Biodegradable Synthetic Polymer in High-Speed Spinning and Underpressure Spunbonding Process

A new biodegradable synthetic polyesteramid (PEA) was characterized by means of thermogravimetry (TG) differential scanning calorimetry (DSC) and dynamic rheological measurements. Two glass transition ranges at about –33 and 38°C and a melting enthalpy of 33 J/g were measured, indicating that PEA is an immiscible blend of two components with a small crystalline part. The material was spun in a high-speed spinning process within the range of 2,000–6,000 M/min and an underpressure spunbonding process within the range of 3,600–7,700 M/min. The textile physical properties of the fibers were 100 MPa tenacity at an elongation at break of 30%, and an E-modulus of 0.5 GPa. The mass per unit area of the spunbonded nonwovens ranged from 70–159 g/M ². The strength of the spunbonded nonwovens was 28–51 N and 42–74 N in machine and cross direction, respectively. The air permeability of the nonwovens decreased at high air velocities and more fineness of the filaments from 1240–380 l/M ² s.     

Linking field experiments to long-term simulation of impacts of nitrogen deposition on heathlands and moorlands

The results from three long-term field manipulation studies of the impacts of increased nitrogen deposition (0–120 kg N ha^–1 yr^–1) on lowland and upland heathlands in the UK were compared, to test if common responses are observed. Consistent increases in Calluna foliar N content and decreases in litter C:N ratios were found across all sites, while increases in N leaching were not observed at any site over the range 0–80 kg ha^–1 yr^–1. However, the response of Calluna biomass did vary between sites, possibly reflecting site differences in nutrient status and management histories. Five versions of a simulation model of heathland responses to N were developed, each reflecting different assumptions about the fate and turnover of soil N. Model outputs supported the deduction from mass balance calculations at two of the field sites that N additions have resulted in an increase in immobilisation; the latter was needed to prevent the model overestimating measured N leaching. However, this version of the model significantly underestimated Calluna biomass. Model versions, which included uptake of organic N by Callunaand re-mobilisation of N from the soil organic store provided some improvement in the fit between modelled and field biomass data, but re-mobilisation also led to an overestimation of N leaching. Quantification of these processes and their response to increased N deposition are therefore critical to interpreting experimental data and predicting the long-term impacts of atmospheric deposition on heathlands and moorlands.     

Selection of adsorbents for treatment of leachate: batch studies of simultaneous adsorption of heavy metals

The simultaneous adsorption of copper (Cu), cadmium (Cd), nickel (Ni), and lead (Pb) ions from spiked deionized water and spiked leachate onto natural materials (peat A and B), by-product or waste materials (carbon-containing ash, paper pellets, pine bark, and semi-coke), and synthetic materials (based on urea-formaldehyde resins, called blue and red adsorbents) or mixtures thereof was investigated. The adsorbents that gave the highest metal removal efficiencies were peat A, a mixture of peat B and carbon-containing ash, and a mixture of peat A and blue. At an initial concentration of 5 mg/l for each metal, the removal of each species of metal ion from spiked water and spiked leachate solutions was very good (>90%) and good (>75%), respectively. When the initial concentration of each metal in the solutions was twenty times higher (100 mg/l), there was a noticeable decrease in the removal efficiency of Cu²⁺, Cd²⁺, and Ni²⁺, but not of Pb²⁺. Langmuir monolayer adsorption capacities, q_m, on peat A were found to be 0.57, 0.37, and 0.36 mmol/g for Pb²⁺, Cd²⁺, and Ni²⁺, respectively. The order of metal adsorption capacity on peat A was the same in the case of competitive multimetal adsorption conditions as it was for single-element adsorption, namely Pb²⁺ > Cd²⁺ ≥ Ni²⁺. The results show that peat alone (an inexpensive adsorbent) is a good adsorbent for heavy metal ions.     

Design parameters for fixed bed reactors of activated carbon developed from fertilizer waste for the removal of some heavy metal ions

Activated carbon, developed from fertilizer waste, has been used for the removal of Hg²⁺, Cr⁶⁺, Pb²⁺, and Cu²⁺. Mass transfer kinetic approach has been successfully applied for the determination of various parameters necessary for designing a fixed-bed absorber. Parameters selected are the length of the (PAZ) primary adsorption zone (δ), total time involved for the establishment of primary adsorption zone (t_x), mass rate of flow to the absorber (F_m), time for primary adsorption zone to move down its length (t_δ), amount of adsorbate adsorbed in PAZ from breakpoint to exhaustion (M_s), fractional capacity (f), time of initial formation of PAZ (t_f) and per cent saturation of column at break point. Chemical regeneration has been achieved with 1 M HNO₃.     

Bacteria Degrading PCBs and CBs Isolated from Long-Term PCB Contaminated Soil

Bacteria able to degrade polychlorinated biphenyls (PCBs) and chlorobenzoic acids (CBs) were isolated from soil that had been contaminated with PCBs for 15–30 years. Contaminated soil in which PCB content ranged between 10–470 mg/kg was naturally vegetated with different plants including ash (Fraxinus excelsior), birch (Betula pendula), black locust (Robinia pseudoacacia), Austrian pine (Pinus nigra) and goat willow (Salix caprea) trees as well as a variety of grasses and forbs. Bacteria able to use biphenyl as a sole source of carbon and energy were found in the root zone of all plants, but occurred in the largest numbers beneath pine and black locust. Bacteria able to degrade chlorobenzoic acids were isolated from the same location contaminated with PCBs. Strains that were taxonomically identified by 16S rDNA as Pandoraea were able to use 2-CB, 3-CB, 2,3-CB, 2,5-CB as sole carbon sources, and the strain Arthrobacter utilised 4-CB.     

Polymer Supported Calix[4]Arene Derivatives for the Extraction of Metals and Dichromate Anions

Three newly synthesized polymer supported calix[4]arene ionophores (7–9) were synthesized, and their ion binding properties toward selected alkali (Li⁺, Na⁺, K⁺, Cs⁺) and transition metal (Hg²⁺, Ni²⁺, Cu²⁺, Co²⁺, Cd²⁺, and Pb²⁺) cations were investigated. It has been observed that these ionophores are not selective toward a particular metal cation but show better ion binding property as compared to monomeric calixarene derivatives (2 and 6). Ionophore 6 and its supported polymer were also employed in dichromate anion extraction experiments. The polymeric ionophore (9) was found an effective extractant for dichromate anion even at pH 7.     

Applying metabolic fingerprinting to ecology: The use of Fourier-transform infrared spectroscopy for the rapid screening of plant responses to N deposition

The potential for metabolic fingerprinting via Fourier-transform infrared (FT-IR) spectroscopy to provide a novel approach for the detection of plant biochemical responses to N deposition is examined. An example of spectral analysis using shoot samples taken from an open top chamber (OTC) experiment simulating wet ammonium deposition is given. Sample preparation involved oven drying and homogenisation via mill grinding. Slurries of a consistent dilution were then prepared prior to FT-IR analysis. Spectra from control, 8 and 16 kg N ha^–1 yr^–1 treatments were then subjected to cross-validated discriminant function analysis. Ordination diagrams showed clear separation between the three N treatments examined. The potential for using Calluna vulgaris (L.) Hull as a bioindicator of N deposition is further evident from these results. The results also clearly demonstrate the power of FT-IR in discriminating between subtle phenotypic alterations in overall plant biochemistry as affected by ammonium pollution.     

The use of silver as a selective precipitant for I in radioactive waste management

¹²⁹I is one of the more hazardous nuclides occurring in radioactive waste. In the form of I⁻, its most likely speciation, it is poorly sorbed on most geologic media. Several workers have suggested the use of silver to precipitate I⁻ as the insoluble AgI, in a cemented waste form, or as a “getter”. The efficacy of this procedure is examined by experiment, in conjunction with thermodynamic predictions.The addition of AgNO₃ to Portland cement leads to coprecipitation with C-S-H, with low Ag solubilities ( 10 μmg/L); 2–;3 orders of magnitude lower than predicted (from Ag₂O). AgI is stable in these matrices, with low aqueous I concentrations (<2 mg/L). In 85% BFS-15% OPC pastes, AgI is unstable due to redox and complexation reactions, with much I⁻ passing into solution; concentrations up to 900 mg/L were observed. It is shown that repository conditions, on closure, are also likely to induce solubilisation of I⁻ from AgI. It is concluded that the use of Ag is unlikely to significantly improve the immobilisation properties of the near field for radioiodine.     

Sorption of strontium on bentonite

Sorption of Sr on bentonite was studied using the batch technique. Distribution coefficients (K_d) were determined as a function of contact time, pH, sorbent and sorbate concentration and temperature. The data were interpreted in terms of Freundlich, Langmuir and Dubinin-Radushkevich isotherms. Thermodynamic parameters for the sorption system were determined at three different temperatures. The positive value of the heat of sorption, ΔH° = 30.62 kJ/mol at 298 K, shows that the sorption of strontium on bentonite is endothermic. The negative value of the free energy of sorption, ΔG° = −10.69 kJ/mol at 298 K, shows the spontaneity of the reaction. ΔG° becomes more negative with increasing temperature, which shows that the sorption process is more favorable at higher temperatures. The mean free energy for sorption, E 9 kJ/mol, suggests that ion exchange is the predominant mode of sorption in the Sr concentration range studied, i.e. 0.01 – 0.3 mol/dm³. The presence of complementary cations depresses the sorption of strontium on bentonite in the order Ca²⁺>Mg²⁺>K⁺>Na⁺. Some organic complexing agents and natural ligands also affect the sorption of strontium. The desorption studies with ground water at low strontium loadings on bentonite show that about 90% of Sr is irreversibly sorbed on the bentonite.     

Field scale N2O flux measurements from grassland using eddy covariance

In order to assess nitrous oxide (N₂O) emissions from typical intensively managed grassland in northern Britain fluxes were measured by eddy covariance using tuneable diode laser absorption spectroscopy from June 2002 to June 2003 for a total period of 4000 h. With micrometeorological techniques it is possible to obtain a very detailed picture of the fluxes of N₂O at field scale (10³–10⁴ m²), which are valuable for extrapolation to regional scales. In this paper three of the four fertilizer applications were investigated in detail. N₂O emissions did not always show a clear response. Hourly fluxes were very large immediately after the June 2002 nitrogen fertilizer application, peaking at 2.5 mg N₂O–N m^–2 s^–1. Daily fluxes were averaging about 300 ng N₂O m^–2 s^–1 over the 4 days following fertilizer application. The response of N₂O emissions was less evident after the August fertilization, although 2 days after fertilizer application an hourly maximum flux of 554 ng N₂O–N m^–2 s^–1 was registered. For the rest of August the flux was undetectable. The differences between fertilization events can be explained by different environmental conditions, such as soil temperature and rainfall. A fertiliser-induced N₂O emission was not observed after fertilizer application in March 2003, due to lack of rainfall. The total N₂O flux from June 2002 to June 2003 was 5.5 kg N₂O–N ha^–1y^–1, which is 2.8% of the total annual N fertilizer input.     

Characterization and phosphate stabilization of dusts from the vitrification of MSW combustion residues

The use of soluble PO₄³⁻ as a heavy metal chemical stabilization agent was evaluated for a dust generated from melting or vitrification of municipal solid waste combustion residues. Vitrification dusts contain high concentrations of volatile elements such as Cl, Na, K, S, Pb, and Zn. These elements are present in the dusts largely as simple salts (e.g. PbCl₂, ZnSO₄) which are highly leachable. At an experimental dose of 0.4 moles of soluble PO₄³⁻ per kg of residue, the pH-dependent leaching (pH 5,7,9) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 100 for many metals; particularly Cd, Cu, Pb and Zn. Bulk and surface spectroscopies showed that the insoluble reaction products are tertiary metal phosphate [e.g. Zn₃(PO₄)₂] and apatite [e.g. Pb₅(PO₄)₃Cl] family minerals. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca²⁺, Zn²⁺, Pb²⁺, Cu²⁺, and Cd²⁺ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids. Soluble phosphate effectively converted soluble metal salts into insoluble metal phosphate phases despite the relatively low doses and dry mixing conditions that were used. Soluble phosphate is an effective stabilization agent for divalent heavy metals in melting dusts where leachable metals are present in high concentrations.     

Deposition and Fate of Lead in a Forested Catchment, Lesni Potok, Central Czech Republic

The deposition of trace elements and their fate in a forest ecosystemhas been monitored at the experimental site, Lesni Potok catchment (LP), with granite bedrock. The catchment is located 30 km ESE from Prague. Annual bulk Pb-deposition flux F_Pb was 3.41 kg km^-2 a^-1 in 1994 and gradually decreased to 0.49 kg km^-2 a^-1 in 2001. The decrease is comparable with those observed in Germany and in the U.S.A. in the 1970s and 1980s. The total sales ban of leaded gasoline in the Czech Republic since January 2001 was accompanied by a pronounced decrease of F_Pb in a single year. The residual Pb-deposition flux is assigned to both the long-range transport of fine-grained vehicular lead aerosol (with a long residence time in the atmosphere) and to theemissions from power plant boilers burning lignite mined in the Czech northwest coal basin. The F_Pb of lead correlates stronglywith those of As, Cd, Cu, Zn and Be, the typical metals in coal fly ash, at two monitored sites. Topsoil horizons contain elevated concentrations of Pb (53–67 mg kg^-1), which are of anthropogenicorigin. Soils in the riparian areas contain increased concentrations of Pb when compared to soils on the hillslope areas. Significant amounts of Pb were found on a stream substrate and Fe-precipitate sampled from the stream. Low concentrations of Pb in bark and bole wood suggest that the uptake of Pb by vegetation is negligible. The very small surface water outputs (average of 0.002 kg km^-2 a^-1) compared to inputs (average of 1.890 kg km^-2 a^-1) from the LP catchment indicate an ongoing accumulation of Pb in a forested landscape.     

Treatment of waste containing EDTA by chemical oxidation

Ethylenediaminetetraacetic acid (EDTA) is a chelating agent that has been extensively used to enhance the solubilization of heavy metal cations and release of EDTA contributes to environmental problems. EDTA is recalcitrant to microbial metabolism and chemical oxidation is considered a possible method of remedial treatment. The use of the commercially available process of MIOX Corporation generates mixed oxidants on site and this solution is markedly effective in the destruction of the chelating characteristic and the decarboxylation of EDTA. When measuring the release of C-14 from carboxyl labeled EDTA, the mixed oxidant solution was comparable to the Fenton's reaction over a broad pH range. The presence of Mn²⁺, Cr³⁺, or Fe³⁺ at levels equal to that of EDTA stimulated the rate of EDTA decomposition; however, the rate of EDTA breakdown was inhibited when the concentration of Cr³⁺ or Mn²⁺ exceeded the concentration of EDTA. The treatment of Co²⁺–EDTA or Cu²⁺–EDTA with mixed oxidants in the presence of ultra violet light resulted in the loss of chelation ability of EDTA. In the absence of chelated metals, over 75% of the chelation property of a 70 mM EDTA solution was destroyed in 45 min. The reaction products resulting from the use of mixed oxidants added to EDTA were non-toxic to bacteria and should not contribute to additional environmental problems.     

Protozooplankton in the Deep Oligotrophic Traunsee (Austria) Influenced by Discharges of Soda and Salt Industries

Traunsee is a deep oligotrophic lake in Austria characterised by an artificial enrichment of chloride in the hypolimnion (up to 170 mg L^-1) caused by waste disposal of soda and salt industries. Protists were collected monthly over one year, observed alive and after Quantitative Protargol Staining (ciliates) or via epifluorescence microscopy (heterotrophic flagellates). Three sites within the lake (0–40 m depths) were compared to deeper water layers from 60–160 m depths where chloride concentrations and conductivity were increased. In addition, we observed the protozooplankton of two neighbouring lakes, i.e. reference systems, during one sampling occasion. In Traunsee the abundance of ciliates was low (200–36 600 cells L^-1) in contrast to high species diversity (at least 60 different species; H_S = 2.6) throughout the year. The main pelagic species in terms of abundance were small oligotrichs and prostomatids like Rimostrombidium brachykinetum/hyalinum, Balanion planctonicum and Urotricha spp. throughout the investigation period. Among free-living heterotrophic flagellates, which occurred at densities of 40–2800 cells mL^-1, small morphotypes dominated in the pelagial. No differences at the community level between the three lakes could be observed and pelagic ciliates and flagellates seemed not to be affected by increased chloride concentrations or by enhanced conductivity.