Characterization of degradation products from alkaline wet oxidation of wheat straw

Alkaline wet oxidation pre-treatment (water, sodium carbonate, oxygen, high temperature and pressure) of wheat straw was performed as a 2(4-1) fractional factorial design with the process parameters: temperature, reaction time, sodium carbonate and oxygen. Alkaline wet oxidation was an efficient pre-treatment of wheat straw that resulted in solid fractions with high cellulose recovery (96%) and high enzymatic convertibility to glucose (67%). Carbonate and temperature were the most important factors for fractionation of wheat straw by wet oxidation. Optimal conditions were 10 min at 195 degrees C with addition of 12 bar oxygen and 6.5 g l(-1) Na2CO3. At these conditions the hemicellulose fraction from 100 g straw consisted of soluble hemicellulose (16 g), low molecular weight carboxylic acids (11 g), monomeric phenols (0.48 g) and 2-furoic acid (0.01 g). Formic acid and acetic acid constituted the majority of degradation products (8.5 g). The main phenol monomers were 4-hydroxybenzaldehyde, vanillin, syringaldehyde. acetosyringone (4-hydroxy-3,5-dimethoxy-acetophenone), vanillic acid and syringic acid, occurring in 0.04-0.12 g per 100 g straw concentrations. High lignin removal from the solid fraction (62%) did not provide a corresponding increase in the phenol monomer content but was correlated to high carboxylic acid concentrations. The degradation products in the hemicellulose fractions co-varied with the pre-treatment conditions in the principal component analysis according to their chemical structure, e.g. diacids (oxalic and succinic acids), furan aldehydes, phenol aldehydes, phenol ketones and phenol acids. Aromatic aldehyde formation was correlated to severe conditions with high temperatures and low pH. Apart from CO2 and water, carboxylic acids were the main degradation products from hemicellulose and lignin.     

Hydrothermal Oxidation of Oily Wastes: an Alternative to Conventional Treatment Methods

Under current legislations most oils used are considered hazardous wastes and its safe collection and disposal must be ensured. Since conventional treatment methods are often inefficient or environmentally unacceptable, the development and application of new technologies is highly necessary. Wet Air Oxidation (WAO) and Supercritical Water Oxidation (SCWO) are two forms of hydrothermal oxidation that have been proved to be effective processes to treat a wide variety of industrial wastes, but they have hardly been tested for oily wastes. In this work, the suitability of hydrothermal oxidation to the treatment of oily wastewaters is described by the results obtained with three different substrates: free fatty acids, cutting oils and bilge wastes. The efficiency of the treatment process is demonstrated for the three oily wastes tested. At temperatures below 350 °C and reaction times of 40 minutes, a 70‐‐90 % of COD elimination is achieved, obtaining an effluent with low molecular weight compounds, mainly carboxylic acids. At 500 °C, a 99 % of COD removal is achieved in less than one minute. At this temperature the reaction seems to proceed mainly through total mineralization to carbon dioxide and water.     

Diamondoids are not forever: microbial biotransformation of diamondoid carboxylic acids

Oil sands process-affected waters (OSPW) contain persistent, toxic naphthenic acids (NAs), including the abundant yet little-studied diamondoid carboxylic acids. Therefore, we investigated the aerobic microbial biotransformation of two of the most abundant, chronically toxic and environmentally relevant diamondoid carboxylic acids: adamantane-1-carboxylic acid (A1CA) and 3-ethyl adamantane carboxylic acid (3EA). We inoculated into minimal salts media with diamondoid carboxylic acids as sole carbon and energy source two samples: (i) a surface water sample (designated TPW) collected from a test pit from the Mildred Lake Settling Basin and (ii) a water sample (designated 2 m) collected at a water depth of 2 m from a tailings pond. By day 33, in TPW enrichments, 71% of A1CA and 50% of 3EA was transformed, with 50% reduction in EC₂₀ toxicity. Similar results were found for 2 m enrichments. Biotransformation of A1CA and 3EA resulted in the production of two metabolites, tentatively identified as 2-hydroxyadamantane-1-carboxylic acid and 3-ethyladamantane-2-ol respectively. Accumulation of both metabolites was less than the loss of the parent compound, indicating that they would have continued to be transformed beyond 33 days and not accumulate as dead-end metabolites. There were shifts in bacterial community composition during biotransformation, with Pseudomonas species, especially P. stutzeri, dominating enrichments irrespective of the diamondoid carboxylic acid. In conclusion, we demonstrated the microbial biotransformation of two diamondoid carboxylic acids, which has potential application for their removal and detoxification from vast OSPW that are a major environmental threat.     

An integrated MBR-TiO2 photocatalysis process for the removal of Carbamazepine from simulated pharmaceutical industrial effluent

This paper aims to demonstrate that integrating biological process and photocatalytic oxidation in a system operated in recycling mode can be a promising technology to treat pharmaceutical wastewater characterized by simultaneous presence of biodegradable and refractory/inhibitory compounds. A lab-scale system integrating a membrane bioreactor (MBR) and a TiO₂ slurry photoreactor was fed on simulated wastewater containing 10 mg/L of the refractory drug Carbamazepine (CBZ). Majority of chemical oxygen demand (COD) was removed by the MBR, while the photocatalytic oxidation was capable to degrade CBZ. CBZ degradation kinetics and its impacts on the biological process were studied. The adoption of a recycling ratio of 4:1 resulted in removal of up to 95% of CBZ. Effluent COD reduction, sludge yield increase and respirometric tests suggested that the oxidation products were mostly biodegradable and not inhibiting the microbial activity. These results evidenced the advantages of the proposed approach for treating pharmaceutical wastewater and similar industrial effluents.     

Pretreatment of wheat straw using combined wet oxidation and alkaline hydrolysis resulting in convertible cellulose and hemicellulose

The wet oxidation process of wheat straw has been studied as a pretreatment method to attain our main goal: To break down cellulose to glucose enzymatic, and secondly, to dissolve hemicellulose (e.g., for fermentation) without producing microbial inhibitors. Wet oxidation combined with base addition readily oxidizes lignin from wheat straw facilitating the polysaccharides for enzymatic hydrolysis. By using a specially constructed autoclave system, the wet oxidation process was optimized with respect to both reaction time and temperature. The best conditions (20 g/L straw, 170 degrees C, 5 to 10 min) gave about 85% w/w yield of converting cellulose to glucose. The process water, containing dissolved hemicellulose and carboxylic acids, has proven to be a direct nutrient source for the fungus Aspergillus niger producing exo-beta-xylosidase. Furfural and hydroxymethyl-furfural, known inhibitors of microbial growth when other pretreatment systems have been applied, were not observed following the wet oxidation treatment. (c) 1996 John Wiley & Sons, Inc.     

Dissimilatory Fe(III) and Mn(IV) reduction.

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process.     

Polystyrene-bound Mn(T4PyP): A highly efficient and reusable catalyst for biomimetic oxidative decarboxylation of carboxylic acids with sodium periodate

In this report, highly efficient oxidative decarboxylation of carboxylic acids with sodium periodate catalyzed by a supported manganese(III) porphyrin is described. In the presence of manganese(III) tetra(4-pyridyl)porphyrin supported on cross-linked chloromethylated polystyrene, [Mn(T4PyP)-CMP], as catalyst, carboxylic acids were converted to their corresponding carbonyl compounds via oxidative decarboxylation with sodium periodate using imidazole as axial ligand. The oxidation of anti-inflammatory drugs such Indomethacin and Ibuprofen was carried out successfully and the decarboxylated products were obtained. This catalyst can be reused several times without loss of its catalytic activity in the oxidation reactions.     

Lipase catalyzed deacidification of tocopherol-rich distillates obtained from natural Vitamin E sources

Taking into account the great interest of consumers for high purity natural vitamin E preparations, it is highly desirable to develop an efficient process for recovering Vitamin E from vegetable oil deodorizer distillates (VODDs) with reduction in costs and better use of energy. The process described herein involves a series of treatment steps, namely desaromatization of VODD, concentration of tocopherols by molecular distillation at high vacuum, lipase catalyzed ester synthesis, and brightening of the resulting tocopherol-rich concentrate with an ethanol (96%):water 60:40 mixture which are similar to conventional processes but the purpose and order of execution of some of them are clearly different. Moreover, some treatment steps were shortened or directly removed. By this process a fully translucent and fluid product was obtained which had tocopherol richness near to the standardized level of 50% concentration, acidity around 1% and a content of emulsifying mono- and diglycerides of 20%. The mixture of mono- and diglycerides that result from the enzymatic process could facilitate absorption of tocopherols by the body and thereby enhancing the biological activity of these compounds. Because all these facts the process presented is feasible as a new industrial purification method of tocopherols from VODDs.     

Deterrent effect of carboxylic acids on cabbage root fly oviposition

In laboratory experiments, 11 selected carboxylic acids were tested to determine which part of the sinapic acid molecule is responsible for deterring cabbage root fly from laying its eggs on otherwise-acceptable cauliflower host-plants. The deterrent effect was only obtained with compounds containing at least one carboxylic group in the molecule. Hence, the aliphatic acids were as deterrent as the aromatic acids to the fly and all the carboxylic acids were as deterrent as sinapic acid, reducing oviposition by > 50%. The inclusion of two carboxylic groups in the molecule, (e.g. phthalic acid and oxalic acid) did not increase the deterrent effect observed with sinapic acid. Some of the long chain fatty acids, with low volatility, low water solubility and thus greater persistence, offer practical opportunities for deterring Delia radicurn from laying its eggs on plants in the field.     

The mechanism underlying the hypolipemic effect of perfluorooctanoic acid (PFOA), perfluorooctane sulphonic acid (PFOSA) and clofibric acid.

The influence of the peroxisomal proliferators perfluorooctanoic acid (PFOA), perfluorooctane sulphonic acid (PFOSA) and clofibric acid on lipid metabolism in rats was studied. Dietary treatment of male Wistar rats with these three compounds resulted in rapid and pronounced reduction in both cholesterol and triacylglycerols in serum. The concentration of liver triacylglycerols was increased by about 300% by PFOSA. Free cholesterol was increased by both perfluoro compounds. Cholesteryl ester was reduced to 50% by PFOSA as well by clofibrate. In hepatocytes from fed rats, all the compounds resulted in reduced cholesterol synthesis from acetate, pyruvate and hydroxymethyl glutarate, but there was no reduction of synthesis from mevalonic acid. The oxidation of palmitate was also increased in all groups. The perfluoro compounds, but not clofibrate, caused some reduction in fatty acid synthesis. The activity of liver HMG-CoA reductase was reduced to 50% or less in all treatment groups and all three compounds led to lower activity of acyl-CoA:cholesterol acyltransferase (ACAT). Changes in other enzymes related to lipid metabolism were inconsistent. The present data suggest that the hypolipemic effect of these compounds may, at least partly, be mediated via a common mechanism; impaired production of lipoprotein particles due to reduced synthesis and esterification of cholesterol together with enhanced oxidation of fatty acids in the liver.     

Transformations of Halogenated Aromatic Aldehydes by Metabolically Stable Anaerobic Enrichment Cultures

Metabolically stable enrichment cultures of anaerobic bacteria obtained by elective enrichment of sediment samples from the Baltic Sea and Gulf of Bothnia have been used to study the oxidation and reduction of the aldehyde group of various halogenated aromatic aldehydes. During the transformation of 5- and 6-chlorovanillin, 6-bromovanillin, 3-chloro-4-hydroxybenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, and 3,5-dibromo-4-hydroxybenzaldehyde, it was shown that synthesis of the corresponding carboxylic acids, which were the principal metabolites, was invariably accompanied by partial reduction of the aldehyde to a hydroxymethyl group in yields of between 3 and 30%. Complete reduction to a methyl group was observed with some of the halogenated vanillins, but to an extremely limited extent with the halogenated 4-hydroxybenzaldehydes. One consortium produced both the hydroxymethyl and methyl compounds from both 5- and 6-chlorovanillin: it was therefore assumed that the methyl compound was the ultimate reduction product. On the basis of the kinetics of formation of the metabolites, it was concluded that the oxidation and reduction reactions were mechanistically related. In addition to these oxidations and reductions, dehalogenation was observed with one of the consortia. In contrast to the transformations of 5- and 6-chlorovanillin, which produced chlorinated methylcatechols, the corresponding compounds were not observed with 5- and 6-bromovanillin: the former was debrominated, forming 4-methylcatechol, whereas the latter produced 6-bromovanillyl alcohol without demethylation. Similarly, although 3-chloro-4-hydroxybenzaldehyde formed the chlorinated carboxylic acid and the benzyl alcohol, the 3-bromo compound was debrominated with formation of 4-hydroxybenzoic acid and, ultimately, phenol. On prolonged incubation, the halogenated carboxylic acids were generally decarboxylated, so that the final products from these substrates were halogenated catechols or phenols. Reductive processes of the type revealed in this study might therefore plausibly occur in the environment during anaerobic transformation of halogenated aromatic aldehydes containing hydroxyl and/or methoxyl groups.     

Mouse hepatic microsomal oxidation of aliphatic aldehydes (C8 to C11) to carboxylic acids.

Addition of saturated and alpha, beta-unsaturated aliphatic aldehydes (C8 to C11) significantly increased NADPH oxidation with mouse hepatic microsomes, and the aldehydes themselves were oxidized to the corresponding carboxylic acids. When these aldehyde substrates were incubated similarly under oxygen-18 gas and the carboxylic acids formed were analyzed by GC-MS after methylation, it was indicated that oxygen-18 was significantly incorporated into the carboxylic acids formed from alpha, beta-unsaturated aldehydes, but not significantly into the carboxylic acids formed from saturated aldehydes. These results indicate that enzyme and/or mechanism responsible for the oxidation of these two types of aldehydes is different from each other.     

Bioremediation of phenolic compounds having endocrine-disrupting activity using ozone oxidation and activated sludge treatment

The bioremediation of water system contaminated with phenolic compounds having endocrine-disrupting activity,i.e. 2,4-dichlorophenol, 2,4-dichlorophenoxy acetic acid (2,4-D), and 2,4,5-trichlorophenoxy acetic acid (2,4,5-T), was investigated by using ozone oxidation and activated sludge treatment. Ozone oxidation (ozonation time: 30 min) followed by activated sludge treatment (incubation time: 5 days) was an efficient treatment method for the conversion of phenolic compounds in water into carbon dioxide and decreased the value of total organic carbon (TOC) up to about 10% of initial value. Furthermore, 2,4-D was dissolved in water containing salt,i.e. artificial seawater (ASW), and this water was used as model coastal water contaminated with phenolic compounds. The activated sludge treatment (incubation time: 5 days) could consume significantly organic acids produced from 2,4-D in the model costal water by the ozone oxidation (ozonation time: 30 min) and decrease the value of TOC up to about 35% of initial value.     

Impacts of drinking water pretreatments on the formation of nitrogenous disinfection by-products

The formation of disinfection by-products (DBPs), including both nitrogenous DBPs (N-DBPs) and carbonaceous DBPs (C-DBPs), was investigated by analyzing chlorinated water samples following the application of three pretreatment processes: (i) powdered activated carbon (PAC) adsorption; (ii) KMnO(4) oxidation and (iii) biological contact oxidation (BCO), coupled with conventional water treatment processes. PAC adsorption can remove effectively the precursors of chloroform (42.7%), dichloroacetonitrile (28.6%), dichloroacetamide (DCAcAm) (27.2%) and trichloronitromethane (35.7%), which were higher than that pretreated by KMnO(4) oxidation and/or BCO process. The removal efficiency of dissolved organic carbon by BCO process (76.5%)--was superior to that by PAC adsorption (69.9%) and KMnO(4) oxidation (61.4%). However, BCO increased the dissolved organic nitrogen (DON) concentration which caused more N-DBPs to be formed during subsequent chlorination. Soluble microbial products including numerous DON compounds were produced in the BCO process and were observed to play an essential role in the formation of DCAcAm in particular.     

Enantioselective kinetic resolution of phenylalkyl carboxylic acids using metagenome‐derived esterases

Enantiomerically pure β-arylalkyl carboxylic acids are important synthetic intermediates for the preparation of a wide range of compounds with biological and pharmacological activities. A library of 83 enzymes isolated from the metagenome was searched for activity in the hydrolysis of ethyl esters of three racemic phenylalkyl carboxylic acids by a microtiter plate-based screening using a pH-indicator assay. Out of these, 20 enzymes were found to be active and were subjected to analytical scale biocatalysis in order to determine their enantioselectivity. The most enantioselective and also enantiocomplementary biocatalysts were then used for preparative scale reactions. Thus, both enantiomers of each of the three phenylalkyl carboxylic acids studied could be obtained in excellent optical purity and high yields.     

Oxidation of lactose with bromine

Oxidation of lactose by bromine in an aqueous buffered solution was conducted as a model experiment to examine the glycosidic linkage cleavage occurring during the oxidation of oligosaccharides and polysaccharides. The resulting oxidation products, after reduction with sodium borodeuteride, were characterized by GLC-MS analyses of the per-O-methyl or per-O-Me3Si derivatives. Most of the products were carboxylic acids, of which lactobionic acid was major. Minor products, identified after partial fractionation on a BioGel P-2 column, comprised oxalic acid; glyceric acid; threonic and erythronic acids; tartaric acid; lyxonic, arabinonic, and xylonic acids; galactonic and gluconic acids; galactosylerythronic acid; galactosylarabinonic acid; galactosylarabinaric acid; galacturonosylarabinonic acid; and galactosylglucaric acid. No keto acids were identified. Galactose was detected as 1-deuteriogalactitol, the presence of which, together with the C6 aldonic acids, supported a galactosidic bond cleavage. Galactosylarabinonic acid was the major constituent (7.5%) among minors, and others constituted 0.2-3.7% of the principal lactobionic acid. These products together comprised 29% of the lactobionic acid, more than half (17%) of which were accounted for by the galactosidic linkage cleavage, supporting the significant decrease in molecular weight seen earlier in the bromine-oxidized polysaccharides by glycosidic cleavage.     

Identification of electrophysiologically-active compounds for New World screwworm, Cochliomyia hominivorax, in larval wound fluid

Abstract Acidic and non-acidic fractions from extracts of fluid from sheep wounds infested with larvae of Cochliomyia hominivorax (Coquerel) were analysed by linked gas chromatography and electroantennography in order to detect electrophysiologically-active compounds that could be potential attractants. Responses to twenty-six electrophysiologically-active compounds were observed and, on the basis of electron impact and chemical ionization mass spectrometry and co-chromatography with authentic compounds, twenty-five of these compounds were characterized. The most abundant compounds identified in the larval wound fluid were straight and methyl-branched aliphatic carboxylic acids, ranging from C₂- to C₅-carbon chain length. Butanoic acid, for example, was found to be present at approximately 0.45mg/ml. Aliphatic carboxylic acids with longer chain lengths were also observed but in trace amounts. Three aromatic carboxylic acids, benzoic, phenylethanoic and 3-phenylpropanoic acids were also present but only phenylethanoic and 3-phenylpropanoic acids elicited electroantennographic responses. Phenol and indole were by far the most abundant components of the non-acid fraction of the larval wound fluid with all other components, except δ-valerolactam, present at levels of less than 5% that of phenol which was present at a concentration of 0.05 mg/ml.
Electroantennographic studies of straight-chain aliphatic carboxylic acids showed that pentanoic acid elicited the strongest response from C. hominivorax. Similar studies showed that 1-octen-3-ol elicited stronger responses than 3-methylphenol, indole, phenol or dimethyldisulphide. 3-Methylindole, which was not found in the wound fluid, also elicited a strong response.
The potential behavioural significance of these compounds is discussed in relation to that of known attractants of C. hominivorax and other dipteran pests of mammals.     

Determination of hydroxyoctadecadienoic acids

Oxidation of low-density lipoproteins (LDL) plays a crucial role in inflammatorydiseases and aging. The main oxidation products of LDL are stereoisomeric 9-hydroxy-10,12-octadecadienoic acids (9-HODEs) and 13-hydroxy-9,11-octadecadienoic acids (13-HODEs). Nevertheless the content of HODEs in natural oxidized LDL is low compared to other components, thus determination of HODEs requires a sample enrichment in most cases. Big losses are encountered during the necessary processing due to the instability of HODEs against acidic conditions. Therefore the use of labeled standards is required. Standards with an 18O label in the carboxylic group used previously may partly suffer a loss of the label by exchange with water. In this paper we describe an improved work-up procedure and the preparation of standards labeled with 18O in the hydroxylic group which is not exchangeable.     

Factors controlling anaerobic ammonium oxidation with nitrite in marine sediments

Factors controlling the anaerobic oxidation of ammonium with nitrate and nitrite were explored in a marine sediment from the Skagerrak in the Baltic-North Sea transition. In anoxic incubations with the addition of nitrite, approximately 65% of the nitrogen gas formation was due to anaerobic ammonium oxidation with nitrite, with the remainder being produced by denitrification. Anaerobic ammonium oxidation with nitrite exhibited a biological temperature response, with a rate optimum at 15 degrees C and a maximum temperature of 37 degrees C. The biological nature of the process and a 1:1 stoichiometry for the reaction between nitrite and ammonium indicated that the transformations might be attributed to the anammox process. Attempts to find other anaerobic ammonium-oxidizing processes in this sediment failed. The apparent K(m) of nitrite consumption was less than 3 microM, and the relative importance of ammonium oxidation with nitrite and denitrification for the production of nitrogen gas was independent of nitrite concentration. Thus, the quantitative importance of ammonium oxidation with nitrite in the jar incubations at elevated nitrite concentrations probably represents the in situ situation. With the addition of nitrate, the production of nitrite from nitrate was four times faster than its consumption and therefore did not limit the rate of ammonium oxidation. Accordingly, the rate of this process was the same whether nitrate or nitrite was added as electron acceptor. The addition of organic matter did not stimulate denitrification, possibly because it was outcompeted by manganese reduction or because transport limitation was removed due to homogenization of the sediment.