Shipboard Measurements of Nitrogen Dioxide,Nitrous Acid,Nitric Acid and Ozone in the Eastern Mediterranean Sea

Measurements of nitrogen dioxide, nitrous and nitric acids as well as ozone were made using newly developed instrumentation onboard the research vessel Aegeon in the Aegean Sea between 25th–29th July 2000. Typical nitrogen dioxide concentrations observed aboard the boat were 4–6 ppb (v/v) with a broad maximum of 20–30 ppb (v/v). Ozone concentrations typically ranged between 40 and 80 ppb (v/v). Mixing ratios of both nitric and nitrous acids in the ambient air of the Aegean Sea were mainly below 50 ppt (v/v). The data also showed a number of short pollution episodes with rapid changes in the concentration of reactive nitrogen compounds [nitrogen dioxide maximum up to 164 ppb (v/v), nitric acid maximum up to 12 ppb (v/v), nitrous acid maximum up to 2.7 ppb (v/v)] and ozone [maximum up to 88 ppb (v/v)]. These episodes were correlated with pollution plumes originating from boats upwind, at short distance, from the R/V Aegeon. The measurements revealed the importance of nitrous and nitric acids for the transport of nitrogen to marine biota in busy ship lanes.     

Valorisation of Vegetal Wastes as a Source of Cellulose and Cellulose Derivatives

Different qualities of CMC were prepared from an agricultural residue (date palm rachis) and a marine waste (Posidonia oceanica). These starting lignocellulosic materials were used as such and after chemical pulping and bleaching. The carboxymethylation reaction was carried out in presence of NaOH (40%) and monochloroacetic acid (ClCH₂COOH, MAC), in n-butanol as the reaction solvent. The substitution degrees (DS) of the obtained CMCs varied from 0.67 to 1.62 and between 0.98 and 1.86, for P. oceanica and date palm rachis, respectively. The CP-MAS ¹³C-NMR spectra of the prepared polyelectrolytes displayed the presence of the main peaks associated with cellulose macromolecules (C1–C6) and that corresponding to carboxyl functions at around 175 ppm. Unfortunately, the peak attributed to methylene groups neighbouring carboxyl moieties are overlapped by C2 and C3, which renders them hardly detectable. Nevertheless, it is worth noting that the CP-MAS ¹³C-NMR spectra revealed the presence of different signals originating from residual impurities (ca. 27 ppm), such as traces of lignin macromolecules (110–150 ppm) and methyl groups attributed to hemicelluloses. Work is in progress to establish a more efficient purification procedure, in order to have more accurate values of DS.     

Preparation of Soybean Oil Polymers with High Molecular Weight

The cationic polymerization of soybean oils was initiated by boron trifluoride diethyl etherate in supercritical carbon dioxide medium. The resulting polymers had molecular weight ranging from 21,842 to 118,300 g/mol. Nuclear magnetic resonance spectroscopy and gel permeation chromatography analysis confirmed the polymerization had occurred. Parameters affecting the polymerization were studied, which included initiator amount and reaction time. Results show that the longer reaction time, up to 3 h, favored the higher molecular weight of polymers at conditions of 140 °C and initiator BF₃·OEt₂ (2.5 g, 0.018 mol). When reaction time was increased further, the molecular weight of polymers stayed the same or slightly decreased. Increased concentration of initiator gave the higher molecular weight of polymers. The high molecular weight polymers were possibly formed through two path ways: polymerization and intermolecular Diels-Alder reaction.     

Effect of Decalin Solvent on the Thermal Degradation of HDPE

The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C₅–C₃₂ yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, α-olefins and α,ω-dienes were detected. Increasing the decalin/plastic ratio led to enhanced α-olefin and n-paraffins yields, but the increase was more significant in the case of α-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical β-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.     

Is The Ca + K + Mg/Al Ratio in the Soil Solution a Predictive Tool for Estimating Forest Damage?

The ratio between (Ca +K +Mg) and Al in nutrientsolution has been suggested as a predictive tool forestimating tree growth disturbance. However, the ratiois unspecific in the sense that it is based on severalelements which are all essential for plant growth;each of these may be growth-limiting. Furthermore,aluminium retards growth at higher concentrations. Itis therefore difficult to give causal and objectivebiological explanations for possible growthdisturbances. The importance of the proportion ofbase-cations to N, at a fixed base-cation/Al ratio, isevaluated with regard to growth of Picea abies.The uptake of elements was found to be selective;nutrients were taken up while most Al remained insolution. Biomass partitioning to the roots increasedafter aluminium addition with low proportions of basecations to nitrogen. We conclude that the low growthrates depend on nutrient limitation in thesetreatments. Low growth rates in the high proportionexperiments may be explained by high internal Alconcentrations. The results strongly suggest thatgrowth rate is not correlated with the ratio in therooting medium and question the validity of usingratios as predictive tools for estimating forestdamage. We suggest that growth limitation of Picea abies in the field may depend on lowproportions of base cations to nitrate. It istherefore important to know the nutritional status ofthe plant material in relation to the growth potentialand environmental limitation to be able to predict andestimate forest damage.     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Mechanism of Microbial Degradation of Slow-Release Fertilizers

Methyleneureas are condensation products of urea and formaldehyde of different molecular mass and solubility; they are used in large amounts both as resins, binders, and insulating materials for industrial applications, as well as a slow-release nitrogen fertilizer for greens, lawns, or in bioremediation processes. In the present study, the microbial breakdown of these products was investigated. The nitrogen was released as ammonia and urea, and the formaldehyde released immediately oxidized via formiate to carbon dioxide. The enzymatic mechanism of metabolization of methyleneureas was studied in microorganisms isolated from soil, which were able to use these compounds as the sole source of nitrogen for growth. A strain of the Gram-negative bacterium Ralstonia paucula (formerly Alcaligenes sp. CDC group IVc-2) completely degraded methylenediurea and dimethylenetriurea to urea, ammonia, formaldehyde, and carbon dioxide. The enzyme initiating this degradation (methylenediurease) was purified and turned out to be different from the previously described enzyme from Ochrobactrum anthropi with regard to its regulation of expression and physicobiochemical properties. Fungal degradation of methyleneureas may occur via the formation of organic acids, thus leading to a nonenzymatic degradation of methyleneureas, which are unstable under acidic conditions.     

Suspension Polymerization of Poly(l-lactide-co-p-dioxanone) in Supercritical Carbon Dioxide

Biodegradable copolymers of l-lactide(l-LA) and p-dioxanone(PDO) were synthesized in supercritical carbon dioxide (scCO₂) with stannous octoate as the ring-opening catalyst and a fluorocarbon polymer surfactant as an stabilizer. Fine powderous products were achieved when more than 90% (w/w) l-LA was fed. Scanning electron micrographic images and laser diffraction particle size analysis of the products showed the mean diameter of particles greatly increased as the content of PDO increased. The obtained polymers had the number-average molecular weights ranging from 15,000 to 26,000 g mol⁻¹ (polydispersity index ranging from 1.3 to 2.1) according to the gel permeation chromatography measurements. The polymer structure was characterized by NMR spectroscopy, indicating the formation of copolymers. Thermal properties of the obtained polymers investigated using differential scanning calorimetry showed that the morphology of products was directly relevant to the crystallinity of the copolymers. The polymerization of l-LA and PDO copolymers in scCO₂ is also proposed as a novel production technique for high-purity, biodegradable polymers.     

Abiotic Hydrolysis of Some Poly-D-glucaramides and Subsequent Microbial Utilization/Degradation

Carbohydrate acid amides, diamides and polyamides have been proposed to be utilized as nitrogen plant fertilizers or fertilizer components, and experiments with Brassica rapa demonstrated a positive biological response when these compounds were used as the only source of fixed nitrogen for plant growth. The present study was carried out with the aim of elucidating the mechanism of degradation of these polymers in both soil/compost and in liquid media and the role of microorganisms in this process. The results obtained suggest that a major route of degradation of polyglucaramides in the environment is their abiotic hydrolysis/release of the diacid and diamine building block units of these polymers, which are then utilized for growth by microorganisms. In cell-free crude extracts from enrichment cultures obtained with different poly-D-glucaramides, no enzyme activities catalyzing the release of diamines from these compounds were detected.     

Biodegradability of Urea-Aldehyde Condensation Products

Condensation products of urea and different aldehydes (formaldehyde, isobutyraldehyde, crotonaldehyde) are used in large amounts (more than 300,000 tons per year) as resins, binders, and insulating materials for industrial applications, as well as in controlled-release nitrogen fertilizer for greens, lawns, or bioremediation processes. The biodegradability of these condensates and the enzymic mechanism of their degradation was studied in mircoorganisms isolated from soil, which were able to use these compounds as the sole source of nitrogen for growth. Different pure cultures of both gram-positive and gram-negative bacteria completely degraded methylenediurea, dimethylenetriurea, isobutylidenediurea, and crotonylidenediurea to urea, ammonia, and the corresponding aldehydes and carbon dioxide. Enzymes initiating this degradation were purified and characterized and turned out to be different with regard to their regulation of expression, their physicobiochemical properties, and their reaction mechanism.     

Assessment of Several Test Methods for the Determination of the Anaerobic Biodegradability of Polymers

Anaerobic degradation of eight commercially available biodegradable polymers was compared in two anaerobic tests using digestion sludge, according to ISO 11734 and ASTM D.5210-91. Cotton, polyhydroxybutyrate/hydroxyvalerate copolymer (PHB/PHV), starch blend, thermoplastic cellulose acetate, and cellulose acetate fibers proved to be anaerobically degradable, but only a low extent of degradation was found for polylactide, polyvinylalcohol, and polycaprolactone. Both test methods gave the same overall results, but with the ISO medium, longer lag phases and greater ranges of variation in the results were observed. These effects are presumably due to low concentrations of carbon dioxide in the ISO medium. Carbon dioxide has been demonstrated to be essential for the growth of various anaerobic bacteria, notably homoacetogenic and methanogenic bacteria.     

基于固态碳源的自养-异养耦合生物脱氮工艺研究

采用基于固态碳源的厌氧氨氧化与反硝化耦合脱氮工艺处理高氮低碳的金属热处理废水。通过接种城市生活污水处理厂剩余污泥和厌氧氨氧化絮状污泥,研究了以固态碳源（3-羟基丁酸脂和3-羟基戊酸脂共聚物,PHBV）和沸石为组合填料的分区式耦合反应器的启动和运行特性。经过76 d的运行,耦合反应器的总氮去除速率达1.05 kg/（m³·d）,且具有良好的出水COD稳定性。废水经过反应器沸石区后,氨氮去除率达97%,亚硝态氮去除率达81%,而硝态氮去除率几乎为零;经过PHBV区后,硝态氮去除率达76%,亚硝态氮去除率达99%,氨氮去除率达97%。沸石区主要进行厌氧氨氧化反应,PHBV区主要进行反硝化反应,功能分区明确,耦合效果较好。     

Kinetic study of permanganate oxidation of tetrachloroethylene at a high pH under acidic conditions

Since carbon compounds are the main component of dense nonaqueous phase liquids (DNAPLs), the end products of all in situ chemical oxidation (ISCO) will include carbon dioxide. If the production rate of carbon dioxide exceeds the capacity of water to remove the carbon dioxide, degassing will occur. The uncontrolled carbon dioxide gas may change the flow patterns, remobilize the pooled DNAPL, transport DNAPL vapor, and reduce the relative permeability to the aqueous phase. Under high pH buffered conditions, most of the carbon dioxide will be dissolved in water. In this study, potassium permanganate oxidation of tetrachloroethylene (PCE) was conducted using a sodium carbonate buffered solution (1 g/L, pH = 10.6 ± 0.1) at three different temperatures (5, 10, and 20°C) and three potassium permanganate concentrations (0.2, 1, and 5 g/L). Extensive kinetic studies suggest that the overall oxidation is a second‐order reaction and pseudo‐first‐order with respect to PCE and potassium permanganate, respectively. The second‐order rate constant and the activation energy were 0.028 ± 0.001 M^?1s^?1 at 20°C and 43.9 ± 2.85 kJ/M, respectively. This study provides a base for further experimental and field studies on potassium permanganate oxidation of PCE under natural or artificial high pH buffered conditions. © 2004 Wiley Periodicals, Inc.     

Nitrate Remediation: The Importance of the Advanced Nitrogen Cycle in Remedy Selection

Nitrate has become an increased regulatory concern due to gradual deterioration of surface and groundwater quality primarily related to widespread fertilizer use. Remediation of nitrate is a relatively straightforward process; however, nitrate impacts to groundwater are often a symptom of a sustained source from another nitrogen form (e.g., ammonia, ammonium nitrate, urea), analogous to how nonaqueous phase liquid can serve as a long‐term source of volatile organic compounds in groundwater. Understanding the various nitrogen transformation reactions when selecting, implementing, or documenting a remedy associated with nitrate is therefore critical to successfully reaching remedial endpoints. Case studies are presented that highlight in situ remedial successes with nitrogen‐impacted groundwater and discuss the key considerations that should be factored into remedy application. ©2015 Wiley Periodicals, Inc.     

Atmospheric Levels of Nitrogen Oxides at a Greek Oil Refinery Compared with the Urban Measurements in Athens

Oil refining is among the industrial activities that emit considerable amounts of air pollutants into the atmosphere. Nitrogen oxides are important air pollutants that are emitted by oil refineries as products of combustion processes. The ambient air concentrations of nitrogen oxide (NO) and nitrogen dioxide (NO₂) were monitored continuously at a site close to an oil refinery, near the city of Corinth in Greece, during autumn 1997 together with the main meteorological parameters. The contribution of the oil refinery to the measured atmospheric levels of nitrogen oxides was estimated. The ambient air concentration of nitrogen oxides in the area surrounding the oil refinery were generally lower than the ambient air concentrations in the urban area of Athens in Greece, and the NO₂ levels were always below the existing air quality standards. The influence of the refinery emitted NO_x in the photochemical production of ozone seems to be more important in terms of human and vegetation exposure given the high ozone backgrounds measured in the area.     

Construction, Characterization and Biological Activity of Chiral and Thermally Stable Nanostructured Poly(Ester-Imide)s as Tyrosine-Containing Pseudo-Poly(Amino Acid)s

In this paper we studied the synthesis of biodegradable optically active poly(ester-imide)s containing different amino acid residues in the main chain. These pseudo-poly(amino acid)s were synthesized by polycondensation of N,N′-(pyromellitoyl)-bis-l-tyrosine dimethyl ester as a diphenolic monomer and two chiral trimellitic anhydride-derived diacid monomers containing s-valine and l-methionine. The direct polycondensation reaction of these diacids with aromatic diol was carried out in a system of tosyl chloride (TsCl), pyridine (Py) and N,N′-dimethylformamide (DMF) as a condensing agent. The structures and morphology of these polymers were studied by FT-IR, ¹H-NMR, powder X-ray diffraction, field emission scanning electron microscopy (FE-SEM), specific rotation, elemental and thermogravimetric analysis (TGA) techniques. TGA profiles indicate that the resulting PEIs have a good thermal stability. Morphology probes showed these polymers were noncrystalline and nanostructured polymers. The monomers and prepared polymers were buried under the soil to study the sensitivity of the monomers and the obtained polymers to microbial degradation. The high microbial population and prominent dehydrogenase activity in the soil containing polymers showed that the synthesized polymers are biologically active and microbiologically biodegradable. Wheat seedling growth in the soil buried with synthetic polymers not only confirmed non-toxicity of polymers but also showed possibility of phyto-remediation in polymer-contaminated soils.     

Determination of In Situ Esterification Parameters of Citric Acid-Glycerol Based Polymers for Wood Impregnation

The development of wood treatments is of increasing industrial importance. A novel technique for improving the properties of lodgepole pine and white pine through modification of the microstructure is described. The present investigation is devoted to the synthesis and determination of in situ parameters of citric acid and glycerol based polymers for wood impregnation. This solvent free approach is environmentally friendly and achieved through an esterification condensation reaction under acidic conditions. Crude glycerol and citric acid reactants were cross-linked via a curing process at 160?°C creating a polymer with only water as the byproduct. The ester bonds and crosslinking levels were controlled using different catalysts and citric acid contents and related to the reaction time and temperature. The nature of bonding within the polymers and at the wood cell walls was determined by FT-IR analysis. The thermal properties such as glass transition temperature (T_g) were studied using TGA/DSC and the effect of citric acid content and catalyst type determined. Dimensional stability of impregnated wood samples improved above 50% for each sample with HCl and p-TSA catalysts compared to control samples. FTIR spectra were studied to show the presence of the ester linkages of the polymer in situ at the wood cell walls. Bonding between the polymer and wood macromolecules were observed by scanning electron microscopy and interpreted as evidence of chemical bonds at the wood cells. When prepared using a catalyst, the polymer was intimately incorporated into wood structure significantly improving the substrate dimensional stability. Enhanced stability makes this approach of particular interest for exterior wood products especially as a green renewable option for the wood industry.     

Anaerobic microbial degradation of poly (3-hydroxyalkanoates) with various terminal electron acceptors

The microbial degradation of poly (3-hydroxyalkanoates) (PHAs) under anaerobic conditions with various terminal electron acceptors was examined. Nitrate-reducing consortia were established using activated sludge, and PHAs were shown to be biodegradable under these conditions. A positive correlation between carbon dioxide production and nitrate reduction was demonstrated. Nitrous oxide accumulated as the main N-containing product of nitrate reduction. The amount of PHAs in activated sludge cultures decreased approximately 20% within 40 days of incubation. Attempts were made to establish iron- and sulfate-reducing consortia from spring water, yet it could not be demonstrated that the mixed cultures were capable of degrading PHAs. Pure cultures of iron- and sulfate-reducing bacteria could not utilize PHAs as sole carbon sources. Methanogenic environments sampled included pond sediment and rumen fluid. PHAs were fermented to methane and carbon dioxide after 10 weeks by a sediment consortium, with 43 to 57% of the substrate carbon transformed to methane. Although it could not be demonstrated that PHAs were biodegraded by a rumen fluid consortium, a facultative anaerobic bacterium, identified as aStaphylococcus sp., that could grow on PHAs was isolated from rumen fluid.     

Syntheses of Biodegradable Functional Polymers by Radical Ring-Opening Polymerization of 2-Methylene-1,3,6-trioxocane

2-Methylene-1,3,6-trioxocane (MTC) was polymerized via ring-opening in the presence of a radical initiator and the obtained polyester was biodegradable. MTC could also copolymerize with various vinyl monomers such as styrene, vinyl acetate, methyl vinyl ketone, N-vinyl-2-pyrrolidone, N-isopropyl acrylamide, and maleic anhydride. By copolymerizing MTC with these vinyl monomers in the presence of a radical initiator, we could obtain various biodegradable polymers with ester group introduced into the backbone. In addition the obtained copolymers exhibit certain functionalities such as photolysis, water-solubility, thermosensitivity, detergent builder, and water-absorbability.     

Improved method for the formation of recycled resins from depolymerized products of waste fiber-reinforced plastics: simple and effective purification of recovered monomers by washing with water

The synthesis of recycled plastics from recovered monomeric materials obtained from the depolymerization reaction of fiber-reinforced plastics (FRP) was examined. The depolymerization reaction of FRP in the presence of N,N-dimethylaminopyridine (DMAP) smoothly yielded the corresponding monomers, which mainly consisted of dimethyl phthalates. The polymerization reaction with this monomer failed to form the corresponding unsaturated polyesters due to contamination by N-methyl-4-pyridone, a decomposition product of DMAP. An efficient purification of the recovered monomer was achieved by washing with water, and the purified monomer successfully yielded the corresponding polymers. A hardness test revealed that the polymers were as hard as the polyester made from virgin materials. The present modification provides a practical method for the preparation of recycled plastics from depolymerized plastics.