Effects of Nitrogen Deposition on Bryophyte Species Composition of Calcareous Grasslands

Regular additions of NH₄NO₃ (35–140 kg N ha⁻¹ yr⁻¹) and (NH₄)₂SO₄ (140 kg N ha⁻¹ yr⁻¹) to a calcareous grassland in northern England over a period of 12 years have resulted in a decline in the frequency of the indigenous bryophyte species and the establishment of non-indigenous calcifuge species, with implications for the structure and composition of this calcareous bryophyte community. The lowest NH₄NO₃ additions of 35 kg N ha⁻¹ yr⁻¹ produced significant declines in frequency of Hypnum cupressiforme, Campylium chrysophyllum, and Calliergon cuspidatum. Significant reductions in frequency at higher NH₄NO₃ application rates were recorded for Pseudoscleropodium purum, Ctenidum molluscum, and Dicranum scoparium. The highest NH₄NO₃ and (NH₄)₂SO₄ additions provided conditions conducive for the establishment of two typical calcifuges – Polytrichum spp. and Campylopus introflexus, respectively. Substrate-surface pH measurements showed a dose-related reduction in pH with increasing NH₄NO₃ deposition rates of 1.6 pH units between the control and highest deposition rate, and a further significant fall in pH, of >1 pH unit, between the NH₄NO₃ and (NH₄)₂SO₄ treatments. These results suggest that indigenous bryophyte composition may be at risk from nitrogen deposition rates of 35 kg N ha⁻¹ yr⁻¹ or less. These effects are of particular concern for rare or endangered species of low frequency.     

Chemical Recycling of Polyamide Waste at Various Temperatures and Pressures Using High Pressure Autoclave Technique

Chemical recycling of polyamide waste in water was studied using 0.5 L high pressure autoclave at temperatures of 150, 200, 210, 220,230 and 240 °C and at various pressures of 100, 200, 300, 400, 500, 600 and 700 psi (pound per square inch). Viscosity average molecular weight of the polyamide waste sample was determined by Ostwald method and recorded as 1.928 × 10³. The reaction was found to be first order with velocity constant in order of 10⁻² min⁻¹. The velocity constant and percent conversion of depolymerization reaction at 240 °C and 700 psi pressure were recorded as 2.936 × 10⁻² min⁻¹ and 99.99% respectively. The velocity constant was obtained on the basis of measurement of amine value. Kinetic and thermodynamic parameters such as energy of activation, frequency factor, enthalpy of activation were found to be 10.6 kJ mole⁻¹, 0.3719 min⁻¹ and 6.3 kJ mole⁻¹ respectively, at the optimum conditions for maximum depolymerization of polyamide waste.     

Decomposition of dichloromethane and in situ alkali absorption of resulting halogenated products by a packed-bed non-thermal plasma reactor

For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al₂O₃ particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)₂ was doped onto the surface of α-Al₂O₃ particles, in order to remove halogenated products by in situ absorption with Ca(OH)₂. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH₂Cl₂), and 500 ppm of the initial concentration of CH₂Cl₂ was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10⁻⁶ m³ min⁻¹ at room temperature. As a result, it was recognized that the amount of CH₂Cl₂ decomposed by non-thermal plasma in an α-Al₂O₃ particle bed increased with an increase in plasma input power. The ratio of decomposition of CH₂Cl₂ was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO₂, CH₃Cl, COCl₂, HCl, and Cl₂ were observed as the major reaction products. On the other hand, when CH₂Cl₂ was introduced into the plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ were packed, the ratio of decomposition of CH₂Cl₂ became higher, compared to the case that α-Al₂O₃ particles were not doped with Ca(OH)₂. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)₂·4H₂O were detected on Ca(OH)₂ by X-ray diffraction. From these findings, it was recognized that CH₂Cl₂ was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ sorbent were packed.     

Quantification of multiple methane emission sources at landfills using a double tracer technique

A double tracer technique was used successfully to quantify whole-site methane (CH₄) emissions from Fakse Landfill. Emissions from different sections of the landfill were quantified by using two different tracers. A scaled-down version of the tracer technique measuring close-by to localized sources having limited areal extent was also used to quantify emissions from on-site sources at the landfill facility, including a composting area and a sewage sludge storage pit. Three field campaigns were performed. At all three field campaigns an overall leak search showed that the CH₄ emissions from the old landfill section were localized to the leachate collection wells and slope areas. The average CH₄ emissions from the old landfill section were quantified to be 32.6 ± 7.4 kg CH₄ h⁻¹, whereas the source at the new section was quantified to be 10.3 ± 5.3 kg CH₄ h⁻¹. The CH₄ emission from the compost area was 0.5 ± 0.25 kg CH₄ h⁻¹, whereas the carbon dioxide (CO₂) and nitrous oxide (N₂O) flux was quantified to be in the order of 332 ± 166 kg CO₂ h⁻¹ and 0.06 ± 0.03 kg N₂O h⁻¹, respectively. The sludge pit located west of the compost material was quantified to have an emission of 2.4 ± 0.63 kg h⁻¹ CH₄, and 0.03 ± 0.01 kg h⁻¹ N₂O.     

The Transit of 35SO4 2- and 3H2O Added In Situ to Soil in a Boreal Coniferous Forest

A solution containing ³⁵SO₄ ^2- and ³H₂O was applied to four plots (5 × 5 m) in a boreal coniferous forest in the Laflamme Lake watershed, Québec, under two contrasting conditions: in summer (plots 1 and 2), and on the snowpack before snowmelt (plots 3 and 4). The transit of both these tracers in the soil solution was then followed through a network of soil lysimeters located at different depths. Four months after the summer application, ³H₂O had infiltrated the whole soil profile at plot 1, while ³⁵SO₄ ^2- was only observed in the LFH and Bhf horizons. A ³⁵SO₄ ^2- budget calculated from mid-August to November indicated that 89 and 10.6% of the added ³⁵SO₄ ^2- was retained within the LFH and the Bhf layers, respectively. Fifteen months later, the added ³⁵SO₄ ^2- was distributed in the following proportions within the soil horizons: LFH (73.7%), Bhf (11.8%) and Bf (12.8%), for a total retention rate of 98.3%. The superficial penetration of ³H₂O at plot 2 was indicative of a major lateral water movement that prevented the calculation of a ³⁵SO₄ ^2- budget. This situation also was observed at plot 4 during snowmelt. At plot 3, ³H₂O moved freely through the soil profile and a significant fraction of the added ³⁵SO₄ ^2- reached the B horizons, where it was presumably adsorbed on aluminum (Al) and ferric (Fe) oxides. The ³⁵SO₄ ^2- budget for plot 3 from March to November indicated that 87% of the added ³⁵SO₄ ^2- was retained within the soil profile, with most being retained in the B horizons (LFH = 33.1%, Bhf = 33.1%, Bf = 20.8%). The contrasting retention patterns of ³⁵SO₄ ^2- within the soil profile following the summer addition and snowmelt likely was caused by the contrastingsoil temperatures and soil solution residence times within the differentsoil layers. The persistence of ³⁵SO₄ ^2- in the soil solution of the entire profile long after the initial tracer infiltration, and the relative temporal stability of specific activity of SO₄ ^2-, point to the establishment of an isotopic equilibrium between the added ³⁵SO₄ and the active S-containing reservoirs within a given soil horizon. Overall, the results clearly illustrate the very strong potential for ³⁵SO₄ ^2- retention and recycling in forest soils.     

Nutrient release from bisulfate-amended phytase-diet poultry litter under simulated weathering conditions

Poultry litter generated on the Delmarva Peninsula is from phytase-modified bird diet and bisulfate amendment. To establish agronomic application rates in conservation tillage systems, bisulfate-amended phytase-diet poultry litter was investigated for its nutrient release kinetics and supply capacity under simulated weathering conditions. Delmarva poultry litter was packed in PVC columns (15 cm i.d. × 25 cm height) to a depth of 5 cm and leached intermittently with 600 mm of water for 190 days. Concentrations of various nutrients in leachate were analyzed and nutrient release kinetics were modelled. Poultry litter leachate contained high contents of dissolved organic carbon (DOC, 35–11,800 mg L^?1), nitrogen (N 6–2690 mg L^?1), phosphorus (P 45–225 mg L^?1), potassium (K 20–6060 mg L^?1), and other nutrients. Release of the nutrients occurred primarily in the starting 5 weeks and mostly followed a first order Exponential-Rise-to-Maximum model. Under the specified conditions, the poultry litter demonstrated a nutrient supply capacity of 11.7 kg N Mg^?1, 5.4 kg P Mg^?1, and 36.8 kg K Mg^?1. Release of the potentially plant-available N and K was nearly finalized within 190 days of leaching/weathering, but it would require two years for full release of the leachable P. The results indicate that with consideration of field conditions, surface application of bisulfate-amended phytase-diet Delmarva poultry litter at recommended 6.6 Mg ha^?1 to conservation tillage systems would largely provide P 25.0 kg ha^?1, N 106.6 kg ha^?1, and K 245.5 kg ha^?1 to seasonal crops.     

Degradation of Monophenylheptamethylcyclotetrasiloxane and 2,6-cis-Diphenylhexamethylcycloterasiloxane in Londo Soil

The natural degradation of monophenylheptamethylcyclotetrasiloxane and 2,6-cis-diphenylhexamethylcyclotetrasiloxane in soil was evaluated under laboratory conditions. Both monophenyl and 2,6-cis underwent rapid degradation in dry soil generating the same products in varying proportions. During the first 24 hr, approximately 99% of the two materials underwent significant chemical transformations forming silanols of various structures, dimethyl cyclic siloxanes of the structure (Me₂SiO)x, and rearrangement products (geometrical isomers) of diphenylhexamethylcyclotetrasiloxane. Among the silanols, the following were identified as trimethylsilyl derivatives: HOSiMe₂OH, HOSiMePhOH, HOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OH, HOSiMePhOSiMePhOH, HOSiMe₂OSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OH, HOSiMe₂OSiMePhOSiMe₂OH, HOSiMePhSiMe₂OSiMePhOH, HOSiMePhOSiMePhOSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OSiMe₂OH, HOSiMe₂OSiMePhOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMePhOSiMe₂OH, HOSiMePhOSiMePhOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OSiMePhOH, HOSiMe₂OSiMePh-OSiMePhOSiMe₂OH. Derivatization was carried out using bis(trimethylsilyl)trifluoroacetamide. Gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry (atmospheric pressure chemical ionization) analyses were used to derive structures. Structures were confirmed by gas chromatography-mass spectrometry comparisons of synthetic standards. Degradation was slower in wet soil. Nevertheless, in 14 days, the chemical transformation was essentially found to be complete as soil was allowed to dry. Detection of phenol as one of the degradation products revealed the occurrence of carbon–silicon bond cleavage promoted by soil.     

Simulation of substrate degradation in composting of sewage sludge

To simulate the substrate degradation kinetics of the composting process, this paper develops a mathematical model with a first-order reaction assumption and heat/mass balance equations. A pilot-scale composting test with a mixture of sewage sludge and wheat straw was conducted in an insulated reactor. The BVS (biodegradable volatile solids) degradation process, matrix mass, MC (moisture content), DM (dry matter) and VS (volatile solid) were simulated numerically by the model and experimental data. The numerical simulation offered a method for simulating k (the first-order rate constant) and estimating k₂₀ (the first-order rate constant at 20 °C). After comparison with experimental values, the relative error of the simulation value of the mass of the compost at maturity was 0.22%, MC 2.9%, DM 4.9% and VS 5.2%, which mean that the simulation is a good fit. The k of sewage sludge was simulated, and k₂₀, k_20s (first-order rate coefficient of slow fraction of BVS at 20 °C) of the sewage sludge were estimated as 0.082 and 0.015 d^?1, respectively.     

Study of nitrogen oxide absorption in the calcium sulfite slurry

Experiments were conducted using a bubbling reactor to investigate nitrogen oxide absorption in the calcium sulfite slurry. The effects of CaSO₃ concentration, NO₂/NO mole ratio and O₂ concentrations on NO₂ and SO₂ absorption efficiencies were investigated. Five types of additives, including MgSO₄, Na₂SO₄, FeSO₄, MgSO₄/Na₂SO₄ and FeSO₄/Na₂SO₄, had been evaluated for enhancing NO₂ absorption in CaSO₃ slurry. Results showed that CaSO₃ concentration had significant impact on NO₂ and SO₂ absorption efficiencies, and the highest absorption efficiencies of SO₂ and NO₂ could reach about 99.5 and 75.0 %, respectively. Furthermore, the NO₂ absorption was closely related to the NO₂/NO mole ratio, and the existence of NO₂ in flue gas may promote NO absorption. The presence of O₂ in simulated flue gas was disadvantage for NO _x removal because it can oxidize sulfite to sulfate. It was worth pointing out that FeSO₄/Na₂SO₄ was the best additive among those investigated additives, as the NO₂ removal efficiency was significantly increased from 74.8 to 95.0 %. IC and in situ FTIR results suggest that the main products were NO₃ ^? and NO₂ ^? in liquid phase and N₂O, N₂O₅ and HNO₃ in gas phase during the CaSO₃ absorption process.     

Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10⁻⁴mol/L) and H₂O₂ (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10⁻⁹−6.083 × 10⁻⁹ mol^1.7 L s⁻¹. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H₂O₂ was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.     

Degradation activity of Clostridium species DC-1 in the cis-1,2-dichloroethylene contaminated site in the presence of indigenous microorganisms and Escherichia coli

We showed the cis-1,2-dichloroethylene (cis-1,2-DCE) dechlorination ability of Clostridium species DC-1 in association with other bacteria. Result of denaturing gradient gel electrophoresis showed the dominant band pattern of DC-1 during the degradation time of cis-1,2-DCE and dominance of some other Clostridium species. Experiment with addition of Escherichia coli (E. coli) showed that dechlorinating activity of DC-1 was not inhibited by the presence of E. coli. Pour plate experiment with DC-1 and E. coli revealed that the dominance of Clostridium species caused the decrease of E. coli growth in a bioremediation state. This result suggested the possibility of Clostridium species DC-1 as a degrader of cis-1,2-DCE, in a cis-1,2-DCE contaminated site where an indigenous microbial community is present. Experiment conducting with E. coli suggested that the strain in the contaminated site did not inhibit the degradation of cis-1,2-DCE and during the degradation period, rather some other Clostridium species became dominant and the growth of E. coli would be decreased. This finding could be a very positive approach for implementing the dechlorinating bacteria at aliphatic chlorinated component contaminated sites.     

Limits and dynamics of methane oxidation in landfill cover soils

In order to understand the limits and dynamics of methane (CH₄) oxidation in landfill cover soils, we investigated CH₄ oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO₂ concentration. The results indicate a significant difference between the observed soil CH₄ oxidation at field sampled conditions compared to optimum conditions achieved through pre-incubation (60 days) in the presence of CH₄ (50 ml l⁻¹) and soil moisture optimization. This pre-incubation period normalized CH₄ oxidation rates to within the same order of magnitude (112-644 μg CH₄ g⁻¹ day⁻¹) for all the cover soils samples examined, as opposed to the four orders of magnitude variation in the soil CH₄ oxidation rates without this pre-incubation (0.9-277 μg CH₄ g⁻¹ day⁻¹).Using pre-incubated soils, a minimum soil moisture potential threshold for CH₄ oxidation activity was estimated at 1500 kPa, which is the soil wilting point. From the laboratory incubations, 50% of the oxidation capacity was inhibited at soil moisture potential drier than 700 kPa and optimum oxidation activity was typical observed at 50 kPa, which is just slightly drier than field capacity (33 kPa). At the extreme temperatures for CH₄ oxidation activity, this minimum moisture potential threshold decreased (300 kPa for temperatures <5 °C and 50 kPa for temperatures >40 °C), indicating the requirement for more easily available soil water. However, oxidation rates at these extreme temperatures were less than 10% of the rate observed at more optimum temperatures (∼30 °C). For temperatures from 5 to 40 °C, the rate of CH₄ oxidation was not limited by moisture potentials between 0 (saturated) and 50 kPa. The use of soil moisture potential normalizes soil variability (e.g. soil texture and organic matter content) with respect to the effect of soil moisture on methanotroph activity. The results of this study indicate that the wilting point is the lower moisture threshold for CH₄ oxidation activity and optimum moisture potential is close to field capacity.No inhibitory effects of elevated CO₂ soil gas concentrations were observed on CH₄ oxidation rates. However, significant differences were observed for diurnal temperature fluctuations compared to thermally equivalent daily isothermal incubations.     

Furniture wood wastes: Experimental property characterisation and burning tests

Referring to the industrial wood waste category (as dominant in the provincial district of Pesaro-Urbino, Marche Region, Italy), this paper deals with the experimental characterisation and the carrying out of non-controlled burning tests (at lab- and pilot-scale) for selected “raw” and primarily “engineered” (“composite”) wood wastes.The property characterisation has primarily revealed the following aspects: potential influence on moisture content of local weather conditions at outdoor wood waste storage sites; generally, higher ash contents in “engineered” wood wastes as compared with “raw” wood wastes; and relatively high energy content values of “engineered” wood wastes (ranging on the whole from 3675 to 5105 kcal kg⁻¹ for HHV, and from 3304 to 4634 kcal kg⁻¹ for LHV).The smoke qualitative analysis of non-controlled lab-scale burning tests has primarily revealed: the presence of specific organic compounds indicative of incomplete wood combustion; the presence exclusively in “engineered” wood burning tests of pyrroles and amines, as well as the additional presence (as compared with “raw” wood burning) of further phenolic and containing nitrogen compounds; and the potential environmental impact of incomplete industrial wood burning on the photochemical smog phenomenon.Finally, non-controlled pilot-scale burning tests have primarily given the following findings: emission presence of carbon monoxide indicative of incomplete wood combustion; higher nitrogen oxide emission values detected in “engineered” wood burning tests as compared with “raw” wood burning test; and considerable generation of the respirable PM₁ fraction during incomplete industrial wood burning.     

Effect of aeration modes on the characteristics of composting emissions and the NH3 removal efficiency by using biotrickling filter

A pilot biotrickling filter (BTF) packed with ZX02 fibrous balls as packing material was tested for the treatment of ammonia (NH₃) released from a composting plant of dairy manure. In order to investigate the effects of three compost aeration modes (mode Co-I, Co-II and In-II) on the NH₃ removal efficiency, a field experiment was continuously carried out for more than eight months. The results demonstrated that under the intermittent aeration mode (In-II), the NH₃ removal efficiency reached 99.2 ± 0.1% when the inlet NH₃ concentration was 7.5-32.3 mg m⁻³ (9.8-42.5 ppmv). The maximum and critical elimination capacity of the biotrickling filter was 22.6 and 4.9 g NH₃ m⁻³ h⁻¹, respectively. The effluent concentration of NH₃ was lower than 1.0 mg m⁻³, which meets the first class discharge standards of GB14554-93. When the concentration of free ammonia in the trickling liquid was varied from 0.1 to 0.4 mg L⁻¹, the nitrification yield was between 47.9% and 103.8%. In addition, the optimum liquid tricking velocity (LTV) of the biotrickling filter was 0.5 m³ m⁻² h⁻¹ for low inlet concentrations and 2.2 m³ m⁻² h⁻¹ for high inlet concentrations. Therefore, the use of the biotrickling filter for the compost under the third aeration mode (In-II) yielded an effective optimum NH₃ removal and reduced the nitrogen loss in the compost.