Partial oxidation of n-hexadecane and polyethylene in supercritical water

In this study, we show the results of partial oxidation experiments of n-hexadecane (n-C₁₆) and polyethylene (PE) in supercritical water (SCW). The experiments were carried out at 673 or 693 K of reaction temperature and 5 or 30 min of reaction time using a 6 cm³ of a batch type reactor. Water density ranged from 0.1 to 0.52 g/cm³ (water pressure: 20–40 MPa). The loaded amount of oxygen was set to 0.3 of the ratio of oxygen atom to carbon atom. Some experiments were made using CO instead of oxygen for the partial oxidation of n-C₁₆ and PE to explore the effect of water gas shift reaction. In the results of partial oxidation of n-C₁₆, the yield of CO and some compounds containing oxygen atoms, such as aldehydes and ketones increased with increasing water density. Moreover, 1-alkene/ n-alkane ratio in the products decreased with increasing water density. The 1-alkene/n-alkane ratio was lower than that of pyrolysis in SCW. Also for the case of PE experiments, in dense SCW (0.42 g/cm³), the 1-alkene/n-alkane ratio in partial oxidation was lower than that in SCW pyrolysis. In the case of CO experiments for n-C₁₆ and PE, 1-alkene/n-alkane ratio was a little lower than that of pyrolysis in SCW. These results show that the yield of n-alkane, which is a hydrogenated compound, was higher through water gas shift reaction in SCW and also through partial oxidation in SCW. Therefore, these results suggest the possibility of hydrogenation of hydrocarbon through partial oxidation followed by the water gas shift reaction.     

Sources and Health Risk of Organic Compounds in Respirable Particles in Tehran,Iran

Forty-one respirable particle (PM₄) samples were collected from October 2011 through March 2012. This timespan covered the fall and winter seasons in Tehran, Iran. The associated polycyclic aromatic hydrocarbon (PAH) and n-alkane concentrations were analyzed to investigate the sources of these compounds and health risks of the former. The average total PAH and n-alkane concentrations were 16.2 ng/m³ and 758 ng/m³, respectively. The most abundant PAHs were 2- and 3-ring compounds, while the most abundant n-alkanes were nC₁₆ and nC₁₈. The results of source identification by factor analysis (FA) are consistent with and complementary to those from diagnostic ratios (DRs). The PAH DRs indicate a dominant contribution from pyrogenic sources, in particular diesel engines from local traffic sources, while FA reveals a diesel-fuelled vehicle emission related factor, a gasoline engine emission-related factor, an industrial source factor and a wood combustion, incineration and tire tread source factor. The n-alkane DRs indicate dominant contributions from anthropogenic sources or vehicular emissions, while FA reveals a fossil fuel combustion factor and a biogenic source factor. Although the average BaP concentration was below the Iran Department of Environment's annual average standard of 1 ng/m³, the BaP-equivalent concentration of the PAHs (BaP_PEQ) indicates harmful effects cannot be ruled out. The ICR_L and ICR_U data suggests a potential cancer risk incidence of about 1–54 individuals per million in the population from a lifetime of 70 years inhalation of particle associated PAHs in Tehran. These findings highlight the importance of reducing emissions from traffic, in particular emissions from diesel-fuelled vehicles, in Tehran.     

Surface tension as a limiting factor for aerobic n-alkane biodegradation

A new mathematical model for n-alkane biodegradation in crude oil, heavy oil and paraffinic mixtures is described. The pattern of n-alkane degradation as a function of the inverse of hydrocarbon chain length reported in this paper can be considered as general behaviour for many aerobic n-alkane biodegradation processes. A new interpretation of n-alkane biodegradation as a function of surface tension, is given. A mathematical expression was obtained starting from the degradation values of n-alkane and relative surface tension, which is a parameter independent of fermentation conditions. An interesting parameter, b, was identified which represented the accelerating conversion factor for n-alkane biodegradation. The findings suggested that the n-alkane biodegradation. The findings suggested that he n-alkane biodegradation rate may be affected by the fermentation condition (agitation, aeration, etc.) and by the strain of microorganism, while the behaviour pattern of n-alkane degradation was essentially linked to the substrate characteristics (molecular structure, molecular weight and density).     

Biosynthesis of hydrocarbons in insects: Decarboxylation of long chain acids ton-alkanes inPeriplaneta

The biosynthetic pathway ofn-alkanes was investigated in the cockroachesPeriplaneta americana andPeriplaneta fuliginosa. Both sodium [1-¹⁴C] acetate and randomly tritiated long chain fatty acids were incorporated into the cuticular hydrocarbons of both species. The relative incorporation of acetate into each component of the hydrocarbon fraction was about the same as the relative amount of each component in the fraction. In contrast, [R-³H] hexacosanoic acid was preferentially incorporated inton-pentacosane inP. americana and [R-³H] tetracosanoic acid inton-tricosane inP. fuliginosa. Long chain ketones and secondary alcohols, likely intermediates in the proposed condensation-reduction pathway forn-alkane biosynthesis, were not incorporated into hydrocarbon. Results from experiments with dual labeled lauric aicd were also not consistent with the condensation-reduction pathway. The demonstration of the direct decarboxylation of long chain fatty acids ton-alkanes one carbon unit shorter and the lack of incorporation of proposed intermediates of a condensation-reduction pathway constitute the strongest evidence to date that insects utilize an elongation-decarboxylation pathway forn-alkane biosynthesis.     

Metabolism of alkane by yeast

We demonstrated two NAD⁺-linked alcohol dehydrogenases in cell free extracts ofCandida tropicalis grown onn-tetradecane. Comparative studies of localization, properties and regulation indicate that these enzymes are involved in two different pathways ofn-alkane metabolism, one cytoplasmic and the other mitochondrial. Kinetic properties, such as the variation of the K_m and V_max as a function of substrate chain length of the soluble NAD⁺-linked alcohol dehydrogenase, might involve hydrophobic interactions between the substrate and the enzyme. One of five papers being published from the Symposium “Biochemistry of Hydrocarbon Degradation,” presented at the AOCS Meeting, Chicago, September 1970.     

Reversible Solubilization of Typical Polycyclic Aromatic Hydrocarbons (PAH) by a Gas Switchable Surfactant

Surfactant‐enhanced remediation (SER) is one of the most effective remediation methods for polycyclic aromatic hydrocarbons (PAH) contaminated soils. However, mass deployment of SER has been restricted due to the shortage of the separation, recycle technology of the surfactant and its operation costs. This research mainly studied the reversibility of 2‐n‐lauryl‐1,1,3,3‐tetramethyl guanidine (DTMG) surfactant and its influence on reversible solubilization of typical PAH. Experimental results showed that the reversibility of the DTMG surfactant is excellent. The critical micellar concentration (CMC), surface tension and pH of DTMG in CO₂/N₂ conditions undergo reversible changes promptly. DTMG·CO₂ shows a strong solubilization capacity for PAH; the apparent solubilities of the selected PAH pyrene, phenanthrene and anthracene in 4 mmol/L of DTMG·CO₂ solution were about 32.4, 17.1 and 14.6 times higher than in water, respectively. The corresponding molar solubilization ratios were 5.4 × 10^?3, 2.80 × 10^?2 and 1.1 × 10^?3, much higher than those with DTMG. More than 50 % of the PAH in surfactant solutions could be released through gas control at each surfactant concentration, and improved release efficiency was achieved at low surfactant concentrations. In brief, such results in this work introduce a facile method to meliorate the SER technology.     

Temperature programmed desorption of <Emphasis Type="Italic">n</Emphasis>-hexane and <Emphasis Type="Italic">n</Emphasis>-heptane from MFI and FAU zeolites

TPD studies of n-hexane and n-heptane from NaX, Y and ZSM-5 (Na⁺ or H⁺ exchanged) in the experimental system with a TCD detector were performed, using pure He or He/n-alkane mixture as a carrier gas. The TPD profiles with one desorption peak for Y and two peaks for ZSM-5, measured using He/hydrocarbon mixture, were similar to the previously reported equilibrated thermodesorption results. TPD profiles were accurately fitted with a model based on the equilibrium control of the desorption and the adsorption functions derived from the Langmuir or dual site Langmuir isotherms.     

2,9-Dimethylpicene: Synthesis,Mutagenic Activity,and Identification in Natural Samples

2,9-Dimethylpicene (2,9-DMPic) has been conveniently synthesized via a new route involving oxidative photocyclization of suitable substituted diarylethylenes and has been characterized by high-resolution 400-MHz ¹H-NMR spectroscopy. Furthermore, 2,9-DMPic exhibits a typical line narrowed emission spectrum in n-decane matrix frozen at 15 K (Shpol'skii effect). Its unambiguous identification in a natural sample has been performed by this technique, providing strong evidence for the formation of this compound through aromatization of triterpenoid natural precursors. The mutagenicity of this naturally occurring methylated polycyclic aromatic hydrocarbon (PAH) has been examined in six his ^? strains of Salmonella typhimurium (TA 97, TA 98, TA 100, TA 102, TA 104, TA 1537) in the presence of a hepatic xenobiotic-metabolizing system. While carcinogenic PAH, used as positive controls, showed potent effects in this system, 2,9-DMPic proved completely inactive.     

Monitoring of bioventing process for diesel-contaminated soil by dehydrogenase activity, microbial counts and the ratio ofn-alkane/isoprenoid

Monitoring parameters were evaluated for a bioventing process that was designed to treat soils contaminated with diesel fuel. Statistical analyses were conducted to evaluate correlations between total petroleum hydrocarbon concentrations in the contaminated soil and physico-chemical parameters of soil such as microbial counts, dehydrogenase activity, andn-alkane/isoprenoid ratio. The correlation coefficients (r²) obtained showed that TPH concentrations in the bioventing system were strongly correlated with dehydrogenase activity (DHA), total heterotrophic bacterial count, and hydrocarbon utilizing bacterial count. Thus, it was concluded that these parameters could useful monitoring parameters for soils contaminated with diesel fuel     

GAS-PARTICLE PARTITIONING OF POLYCYCLIC AROMATIC HYDROCARBONS DURING THE SPRING AND SUMMER IN A SUBURBAN SITE NEAR MAJOR TRAFFIC ARTERIES

Concentrations of atmospheric polycyclic aromatic hydrocarbons were measured in a suburban site near major traffic arteries during the period April-August 2006. Total suspended particulate during the sampling period was 65.3 ± 33.9 μ g m^?3. Total PAH concentrations were 63.5 ± 20.1 ng m^?3 in the gaseous phase and 1.4 ± 0.3 ng m^?3 in the particulate phase. Observed concentrations were comparable with previously measured values reported in the literature for urban and suburban sites with a high anthropic influence. PAH concentration diagnostic ratios indicate that, during the spring and summer seasons, vehicular emission was the main source of atmospheric PAHs.

Gas/particle partitioning coefficients K _P were well correlated with both the sub-cooled liquid vapor pressures p _L ⁰ and the octanol-air partition coefficients K _OA . Measured K _P values were in a good agreement with K _P values predicted by applying a literature model, which takes into account both adsorption onto black carbon and absorption into the organic matter.     

LONG TERM MONITORING OF POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) IN BLUE MUSSELS (Mytilus edulis) FROM A REMOTE SCOTTISH LOCATION

Farmed mussels have been collected on a monthly basis since 1999 from a remote site on the west coast of Scotland for polycyclic aromatic hydrocarbon (PAHs) analysis with the aim of establishing background concentrations as a benchmark against which to assess any environmental incident. Total PAH (2- to 6-ring parent and alkylated) concentrations ranged from 12.5 to 151.2 μg kg^?1 wet weight. Seasonal trends were evident with concentrations being significantly higher for samples collected between November and March compared to those collected between April and October. By taking the median of medians for each of these time periods two background concentrations are suggested for the total PAH concentrations (2- to 6-ring PAHs parent and alkylated); for April to October: 31.2 μg kg^?1 wet weight and for November to March: 62.9 μg kg^?1 wet weight. Individual PAH concentrations were mainly below the OSPAR Background Assessment Concentrations (BACs), where they are specified, and were only exceeded for the heavier 4- and 5-ring PAHs (fluoranthene, pyrene, benz[a]anthracene and benzo[a]pyrene) in samples collected between November and March. Differences were also seen in the PAH profiles with season. Mussels collected between November and March had a higher proportion of the heavier PAHs compared to mussels collected in the summer and autumn.     

COD fractionation and parameter estimation for combined sewers by respirometric tests

This paper evaluates the effects of the pipeline retention time in sewer systems and the dilution by stormwater runoff on COD fractions and kinetic parameters of samples from two large‐scale wastewater treatment plants (WWTPs) fed with combined sewers, one collected from adjacent residential areas (Sewer Q) and the other undergoing long pipeline transportation (Sewer B). With four batch tests, COD fractions and kinetic parameters of two sewers were obtained by numerical computation based on activated sludge models (ASMs) modified by a dual hydrolysis mechanism. Long pipeline transportation significantly influenced the content and existence of heterotrophic biomass fractions in sewers, and the percentage of the fraction in Sewer B (17%) was higher than that in Sewer Q (9%). Compared with Sewer Q, long pipeline retention also resulted in lower concentrations of hydrolysable fractions and particulate inert COD in Sewer B, as well as an increase in the hydrolysis rate coefficient of particulate hydrolysable COD from 0.90 day^?1 in Sewer Q to 1.83 day^?1 in Sewer B. Results of samples from Sewer B during a typhoon event showed high variations of COD fractions and parameters, indicating the necessity for COD fractionation and parameter calibration before applying ASMs to wet weather cases. Copyright © 2008 Society of Chemical Industry     

Source characterization and the environmental impact of urban street dusts from Egypt based on hydrocarbon distributions

The aliphatic and aromatic fractions of the extracts of ten street dust (SD) samples collected from eight cities covering a wide geographic area of Egypt were analyzed using gas chromatography with flame ionization detector (GC-FID) and GC-MS to compare their hydrocarbon distributions. To identify their sources, the extracts of the possible source materials were also analyzed. The impact of SDs on the marine environment was investigated in a marine sediment collected from the Western Harbor of Alexandria. The GC-FID profiles of the aliphatic fractions showed considerable differences in the n-alkane distribution that permits the classification of the SDs into five groups. This grouping reflects the environments of the cities in which they are collected. The carbon preference index and the unresolved complex mixture relative to the total resolved peaks values revealed that automobile exhaust is the main source of the hydrocarbons in these SDs with a significant contribution from terrestrial higher plant waxes to group 1 (Nile Delta cities). The sterane and hopane profiles supported this conclusion. The total polycyclic aromatic hydrocarbon (PAH) concentrations ranged from 27 to 379 ng/g (dry wt.) and showed clear differences between the SDs. The lowest and highest concentrations were found in samples from Shebeen and Port Said, respectively. The PAH distribution patterns and the ratio of the sum of combustion specific PAHs to total PAHs in samples from Alexandria, Port Said and Cairo were similar, implying similar sources. PAH ratios indicated a mixture of pyrogenic and petrogenic sources of PAHs in all samples where asphalt and automobile fuel exhaust were the major contributors of PAHs in Alexandria, Port Said, Cairo and Sharm El Sheikh cities. These ratios also indicated the predominance of diesel-operated vehicles to the PAHs signatures of Alexandria, Port Said and Cairo while gasoline emissions influence more strongly the PAH distributions in the SDs from Shebeen, Kafr El Sheikh and Sharkea. The PAH fingerprints excluded fresh oil and tire particles as major contributors. Both SDs and petrogenic sources significantly contributed to the hydrocarbon signature of the marine sediment from the Western Harbor of Alexandria.     

OPTIMIZATION OF LARGE VOLUME INJECTION FOR IMPROVED DETECTION OF POLYCYCLIC AROMATIC HYDROCARBONS (PAH) IN MUSSELS

Detection of PAH of six benzene rings is somewhat troublesome and lowering the limits of detection (LODs) for these compounds in food is necessary. For this purpose, we optimized a Programmable-Temperature-Vaporisation (PTV) injection with Large Volume Injection (LVI) with regard to the GC-MS detection of anthracene, benz[a]anthracene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and dibenzo[a,e]pyrene. The optimization of PTV-LVI for GC-MS analysis included the choice of liner, solvent venting, splitless time, split flow and initial inlet temperature for injection of 25 μ L standard solution and spiked mussel samples. Samples were extracted with Accelerated Solvent Extraction (ASE) followed by two semi-automatic clean-up steps; gel permeation chromatography (GPC) on S-X3 and solid phase extraction (SPE) on pre-packed silica columns, prior to gas chromatography-mass spectrometry (GC-MS) detection. In comparison to traditional splitless injection, LODs were lowered for eighteen PAHs by the use of PTV-LVI ranging from 0.05 μ g kg ^?1 to 1.0 μ g kg^?1 fresh weight. In particular, the LOD of dibenzo[a,e]pyrene was improved by a factor of ten when using the validated PTV-LVI method.     

Preparation and characterization of PVA membrane modified by water‐soluble hyperbranched polyester (WHBP) for the dehydration of n‐butanol

Water‐soluble hyperbranched polyester (WHBP) was synthesized through the esterification reaction of the fourth generation hyperbranched polyester and maleic anhydride. A novel cross‐linked WHBP/PVA membrane was prepared by adding WHBP into poly(vinyl alcohol) (PVA) solution with glutaraldehyde as the cross‐linker. WHBP was characterized by Nuclear Magnetic Resonance and Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR‐FTIR), while WHBP/PVA membranes were characterized by ATR‐FTIR, X‐ray Diffraction, Scanning Electron Microscopy, Thermogravimetric Analysis, mechanical capacity, and water contact angle. Testing results showed that maleic anhydride was grafted on the surface of WHBP; compared with PVA membrane, WHBP/PVA membrane had lower crystallinity, weaker mechanical strength, higher hydrophilicity, and better thermal stability. Sorption and diffusion behaviors of n‐butanol and water in WHBP/PVA membrane were investigated; pervaporation performances of WHBP/PVA membrane were studied through the dehydration of the 90 wt % n‐butanol aqueous solution at 40°C. With an increase of the WHBP content from 0 to 30 wt %, both n‐butanol uptake and n‐butanol diffusion coefficient first decreased then increased; n‐butanol flux first decreased from 10 to 2 g·m^?2·h^?1 then increased to 213 g·m^?2·h^?1; both sorption selectivity and diffusion selectivity first increased then decreased; separation factor first increased from 88 to 1309 then decreased to 16. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43533.     

Urban Stream Vulnerability Toward PAHs and n-Alkanes and Their Source Identification

Monjolinho River is an important water body located in the central urban region of São Paulo State in southeast Brazil. The present work reports a 4-year study related to spatio-temporal distribution and source identification of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in surface water and sediment samples of Monjolinho River. A total of 25 sampling campaigns for water, and 10 sampling campaigns for sediment collection, were performed from 2011 to 2014. In sediment samples, total PAHs were found in the range of 2.25 µg kg^?1–26,253.87 µg kg^?1, while n-alkane concentrations ranged from 0.01 to 165.64 µg kg^?1. Total PAHs' concentration in surface water was in the range of 0.17–1,348.35 ng L^?1, while n-alkanes were detected in the range of 6.17–316.15 µg L^?1. Principal component analysis was used as a statistical tool for summarizing and interpreting a huge quantity of data. It was observed that concentrations of contaminants increased along the river course in urban zone. Distribution indexes were calculated to identify possible sources of carbon pool that pointed towards petrogenic, pyrogenic, and biogenic sources. The overall concentrations of PAHs and n-alkanes were low compared to many previous studies done elsewhere and were mostly below the threshold effects level except in very few occasional cases, while probable effect level was violated in 1 sample during 4 years. Although adverse impacts are unexpected due to overall low contaminant concentrations, unexpected industrial, and sewage discharges make it risky for safer use as a drinking water resource, especially in dry conditions.     

Reactive separation of p-nitro phenol (PNP) from aqueous solution using tri-n-butyl phosphate: equilibrium and COSMO-RS studies

ABSTRACT

The present study is aimed to optimized diluent type, tri-n-butyl phosphate (TBP) composition and temperature for the reactive extraction of p-nitro phenol (PNP) in two different PNP concentration ranges [(0.00036–0.00646) kmol·m^?3 and (0.00646–0.01437) kmol·m^?3] as found in industrial effluents. 1-Octanol is investigated as the best diluent with TBP based on COSMO-RS theory. Equilibrium study based on mass action law is performed to find the insights of extraction mechanisms, equilibrium constant (K = 295.12 k·mol^?1) and stoichiometry (m:n = 1:1) as also confirmed by FTIR. Thermodynamic parameters, enthalpy (ΔH°), and entropy (ΔS°) are determined 27.51 K J mol^?1 and ?50.21 J mol^?1 K^?1, respectively.     

CuO‐filled aminomethylated polysulfone hybrid membranes for deep desulfurization

CuO‐filled aminomethylated polysulfone hybrid membranes were prepared for sulfur removal from gasoline. The as‐prepared membranes were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray diffraction (XRD). The separation performance of the hybrid membranes was evaluated by pervaporation (PV) separation of n‐heptane/thiophene binary mixture. CuO‐filling leads to a decrease in permeation flux. The sulfur‐enrichment factor increased first and then decreased with increasing CuO loading, and it is worth noting that there is a rebound in enrichment factor above 8 wt % CuO loading. Influencing factors such as nitrogen content, feed temperature, sulfur content, and various hydrocarbons on membrane PV performance were also evaluated. Permeation flux of 23.9 kg·μm·m^?2·h^?1 and sulfur‐enrichment factor of 3.9 can be achieved at 4 wt % CuO loading in PV of n‐heptane/thiophene binary mixture with 1500 μg·g^?1 sulfur content. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3718–3725, 2013     

Coupled Transport of Zr(IV) through Tri-n-butylphosphate-Xylene-Based Supported Liquid Membranes

Abstract

The transport of Zr(IV) through tri-n-butylphosphate-xylene-based liquid membranes, supported in a polypropylene hydrophobic microporous film, has been studied. The concentration of HNO₃ in the feed solution and tri-n-butylphosphate (TBP) carrier in the membrane were varied, and the flux and permeability coefficients were determined. The optimum conditions found for maximum flux were determined to be 10 mol/dm³ HNO₃ and 2.93 mol/dm³ TBP with a flux value of 12.9 × 10^?6 mol · m^?2 · s^?1. The solvent extraction study revealed that 1.25 to 3.5 protons are involved in zirconium transport, and that two molecules of TBP are involved in the complex formation. The value of protons involved varies with acid concentration. The zirconium ion transport is coupled with nitrate ions transport.     

COMPARISON OF TWO ANALYTICAL METHODS FOR THE DETERMINATION OF AZAARENES IN ATMOSPHERIC PARTICULATE MATTER

In this paper, the development of an analytical method for the separation and quantification of 20 azaarenes is described. Two methods are compared: high performance liquid chromatography with fluorescence detection (HPLC-fluorescence) and gas chromatography with mass spectrometry detection (GC-MS).

Although HPLC-fluorescence was proven to be the most sensitive method, GC-MS was selected in particular for the efficiency of the separation of the 20 azaarenes. The detection limits of the HPLC-fluorescence and GC-MS methods varied between 0.04 μ g.L^?1 (dibenz[a,c]acridine) and 1.30 μ g.L ^?1 (acridine) and between 1.50 μ g.L ^?1 (benz[c]acridine) and 2.56 μ g.L ^?1 (dibenz[a,c]acridine) respectively.

The GC-MS method was applied to particulate matter (PM ₁₀ ) samples collected over 48–72 h periods between April 2006 and February 2007 in Strasbourg (East of France). Before analysis aerosol samples were Soxhlet extracted and concentrated to a final volume of about 1 mL of hexane.

The seasonally mean concentrations of all azaarenes for this urban site have shown a seasonal variation in which the maximum concentration occurred in the winter (6.0 ng.m ³ ) and the minimum in the summer (0.90 ng.m³). For all the seasons the 2 rings species were the predominant azaarenes while the > 4 rings species were the less abundant.