Monitoring of Phenol in Wastewater Bioremediation by HPLC

Bioremediation emphasizes the detoxification and destruction of toxic substances by microorganisms. Wastewater obtained from an industrial concern was solvent extracted with methyl alcohol and dichloromethane and analysed by GC/MS. Besides phenol, a large variety of organic compounds were detected. Under controlled laboratory conditions, the wastewater was innoculated with a mixed culture of microorganisms specially selected for their abilities to degrade phenol. Samples were collected at regular intervals from the stirred tank bioreactor and analysed for phenol by reverse phase HPLC with a C18 column. Results shows that from an initial phenol concentration of 987 ppm, slightly more than 50% was destroyed within 163 hours. The dry weight of the microorganisms and the plate count (CFU/ml) shows a steady increase from 0.5238 gms to 0.5355 gms and from 1.1E+9 to 1.94E+13 respectively over the same period. This suggested that the phenol was consumed by the microorganisms as the sole carbon source.     

Production of a refined biooil derived by fast pyrolysis of chicken manure with chemical and physical characteristics close to those of fossil fuels

The chemical and physical properties of raw biooils prevent their direct use in combustion engines. We processed raw pyrolytic biooil derived from chicken manure to yield a colorless refined biooil with diesel qualities. Chemical characterization of the refined biooil involved elemental and several spectroscopic analyses. The physical measurements employed were viscosity, density and heat of combustion. The elemental composition (% wt/wt) of the refined biooil was 82.7 % C, 15.3 % H, 0.2 % N and 1.8 % O, no S. Its viscosity was 0.006 Pa.s and a heat of combustion of 43 MJ kg(-1). The refined biooil fraction contains n-alkanes, ranging from n-C(14) to n-C(27), alkenes varying from C(10:1) to C(22:1), and long-chain alcohols. The refined biooil makes a good diesel fuel due to its chemical and physical properties.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure,biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, ¹³C and 1H Nuclear Magnetic Resonance Spectrometry (¹³C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) ¹³C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

Sorption of herbicides in relation to soil variability and landscape position

Using the soil-water sorption partitioning coefficient (Kd), this study quantified the spatial variation of 2,4-D sorption by soil in an undulating-to-hummocky terrain landscape near Minnedosa, MB, Canada. Herbicide sorption was most strongly related to soil organic matter content and slope position, with greatest sorption occurring in lower landscape positions with greater soil organic matter content. The relation between sorption and slope position was more pronounced under conventional tillage (CT) than under long-term zero-tillage (ZT). Using multivariate regression and three independent variables (soil organic matter content, soil clay content and soil pH), the prediction of herbicide sorption by soil was very good for CT (R2 = 0.89) and adequately for ZT (R2 = 0.53).     

Production of a refined biooil derived by fast pyrolysis of chicken manure with chemical and physical characteristics close to those of fossil fuels

The chemical and physical properties of raw biooils prevent their direct use in combustion engines. We processed raw pyrolytic biooil derived from chicken manure to yield a colorless refined biooil with diesel qualities. Chemical characterization of the refined biooil involved elemental and several spectroscopic analyses. The physical measurements employed were viscosity, density and heat of combustion. The elemental composition (% wt/wt) of the refined biooil was 82.7 % C, 15.3 % H, 0.2 % N and 1.8 % O, no S. Its viscosity was 0.006 Pa.s and a heat of combustion of 43 MJ kg^?1. The refined biooil fraction contains n-alkanes, ranging from n-C₁₄ to n-C₂₇, alkenes varying from C_10:1 to C_22:1, and long-chain alcohols. The refined biooil makes a good diesel fuel due to its chemical and physical properties.     

Separation and identification of heterocyclic nitrogen compounds in biooil derived by fast pyrolysis of chicken manure

N-heterocyclics were separated from a biooil, generated by the pyrolysis of chicken manures by column chromatography over neutral alumina and silica, and identified by Pyrolysis Field Ionization Mass Spectrometry (Py-FIMS) and Electrospray Ionization Mass Spectrometry (ESI-MS). Identities of chemical structures, whose presence was indicated by ESI-MS, were confirmed by comparing the Collision-Induced Dissociations (CID's) mass spectra of unknown and standards. The following seven base structures were identified: pyrazine, benzoquinoline, carbazole, phenylpyridine, indole, pyrazole and pyridine. Available hydrogens bonded to ring carbons and nitrogens on the seven N-heterocyclics were increasingly substituted by alkyl groups, mainly methylene groups (m/z 14) to yield mono-, di-, tri- methyl N-heterocyclics. In some instances, longer alkyl chains, such as ethyl, propyl, up to heptyl groups were the substituents.     

Metabolism of nC11 fatty acid fed to Trichoderma koningii and Penicillium janthinellum II: Production of intracellular and extracellular lipids

Abstract

Little is known about the fungal metabolism of nC₁₀ and nC₁₁ fatty acids and their conversion into lipids. A mixed batch culture of soil fungi, T. koningii and P. janthinellum, was grown on undecanoic acid (UDA), a mixture of UDA and potato dextrose broth (UDA+PDB), and PDB alone to examine their metabolic conversion during growth. We quantified seven intracellular and extracellular lipid classes using Iatroscan thin-layer chromatography with flame ionization detection (TLC-FID). Gas chromatography with flame ionization detection (GC-FID) was used to quantify 42 individual fatty acids. Per 150 mL culture, the mixed fungal culture grown on UDA+PDB produced the highest amount of intracellular (531 mg) and extracellular (14.7 mg) lipids during the exponential phase. The content of total intracellular lipids represented 25% of the total biomass-carbon, or 10% of the total biomass dry weight produced. Fatty acids made up the largest class of intracellular lipids (457 mg/150 mL culture) and they were synthesized at a rate of 2.4 mg/h during the exponential phase, and decomposed at a rate of 1.8 mg/h during the stationary phase, when UDA+PDB was the carbon source. Palmitic acid (C_16:0), stearic acid (C_18:0), oleic acid (C_18:1), linoleic acid (C_18:2) and vaccenic acid (C_18:1) accounted for >80% of the total intracellular fatty acids. During exponential growth on UDA+PDB, hydrocarbons were the largest pool of all extracellular lipids (6.5 mg), and intracellularly they were synthesized at a rate of 64 μg/h. The mixed fungal species culture of T. koningii and P. janthinellum produced many lipids for potential use as industrial feedstocks or bioproducts in biorefineries.     

The conversion of chicken manure to bio-oil by fast pyrolysis. III. Analyses of chicken manure, bio-oils and char by Py-FIMS and Py-FDMS

Fast pyrolysis of chicken manure produced the following three fractions: bio-oil Fraction I, bio-oil Fraction II, and a char. In a previous investigation we analyzed each of the four materials by curie-point pyrolysis-gas chromatography/mass spectrometry (CpPy-FDMS). The objective of this article is to report on the analyses of the same chicken manure and the three fractions derived from it by fast pyrolysis. We now used pyrolysis-field ionization mass spectrometry (Py-FIMS) to characterize the three fractions. In addition, the two bio-oil materials were analyzed by pyrolysis-field desorption mass spectrometry (Py-FDMS). The use of both Py-FIMS and Py-FDMS produced signals over significantly wider mass ranges than did CpPy-GC/MS, and so allowed us to identify considerably larger numbers of constituents in each material. Individual compounds identified in the mass spectra were classified into the following twelve compound classes: (a) low molecular weight compounds (< m/z 62); (b) carbohydrates; (c) phenols + lignin monomers; (d) lignin dimers; (e) n-alkylbenzenes; (f) N-heterocyclics; (g) n-fatty acids; (h) n-alkanes; (i) alkenes; (j) sterols; (k) n-diols and (l) high molecular weight compounds (> m/z 562). Of special interest were the high abundances of low-molecular weight compounds in the two bio-oils which constituted close to one half of the two bio-oils. Prominent among these compounds were water, ammonia, acetic acid, acetamide, propyl radical, formamide and hydrogen cyanide. The main quantitative differences between the two bio-oils was that bio-oil Fraction I, as analyzed by the two mass spectrometric methods, contained lower concentrations of low-molecular weight compounds, carbohydrates, and N-heterocyclics than bio-oil Fraction II but was richer in lignin dimers, n-alkylbenzenes and aliphatics (n-fatty acids, n-alkanes, alkenes, and n-diols). Of special interest were the N-heterocyclics in the two bio-oils such as pyrazole, pyrazoline, substituted pyrroles, pyridine and substituted pyridines, substituted methoxazole, substituted pyrazines, indole and substituted indoles. Fatty acids in all four materials ranged from n-C(9) to n-C(33), alkanes from n-C(9) to n-C(40), alkenes from C(10:1) to C(40:1) and diols from n-C(7) to n-C(29). The chicken manure, bio-oil Fraction I, and char each contained about 4% sterols with cholesterol, ethylcholestriene, ergosterol, ethylcholestene, ethylcholesterol and beta -sitosterol as major components. Semi-quantitative estimates of the total materials identified by Py-FIMS were: chicken manure: 61.1%; bio-oil Fraction I: 81.3%; bio-oil Fraction II: 78.6%; char: 61.3%; and by Py-FDMS were: bio-oil Fraction I: 65.4%; bio-oil Fraction II: 70.0%.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure, biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, 13C and 1H Nuclear Magnetic Resonance Spectrometry (13C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) 13C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

Chemical characterization of fatty acids,alkanes, n-diols and alkyl esters produced by a mixed culture of Trichoderma koningii and Penicillium janthinellum grown aerobically on undecanoic acid,potatoe dextrose and their mixture

Little is known about the mixed fungal synthesis of high-value aliphatics derived from the metabolism of simple and complex carbon substrates. Trichoderma koningii and Penicillium janthinellum were fed with undecanoic acid (UDA), potatoe dextrose broth (PDB), and their mixture. Pyrolysis Field Ionization Mass Spectrometry (Py-FIMS) together with ¹H and ¹³C Nuclear Magnetic Resonance (NMR) characterized CHCl₃ soluble aliphatics in the fungal cell culture. Data from NMR and Py-FIMS analysis were complementary to each other. On average, the mixed fungal species produced mostly fatty acids (28% of total ion intensity, TII) > alkanes (2% of TII) > n-diols (2% of TII) > and alkyl esters (0.8% of TII) when fed with UDA, PDB or UDA+PDB. The cell culture accumulated aliphatics extracellularly, although most of the identified compounds accumulated intracellularly. The mixed fungal culture produced high-value chemicals from the metabolic conversion of simple and complex carbon substrates.