Kinetic model for phenolic compound oxidation by Fenton's reagent

A kinetic model is developed for the oxidation of phenolic compounds by Fenton's reagent. In the first stage a rigorous kinetic model is applied to calculate the different kinetic rate constants for the oxidation process of p-hydroxybenzoic acid. In a second phase a competitive method is applied to calculate these kinetic constants for another 10 phenolic compounds present in agroindustrial and pulp paper wastewaters. These 10 phenolic compounds were: beta-resorcylic acid, 3-(4-hydroxyphenyl)-propionic acid, ferulic acid, protocatechuic acid, caffeic acid, p-coumaric acid, vanillic acid, syringic acid, veratric acid and 3,4,5-trimethoxybenzoic acid.     

Chemical and biological characterization of dissolved organic matter from silver fir and beech forest soils

Despite a growing attention to the dissolved organic matter (DOM) in terrestrial ecosystems and evidence of the fact that vegetation affects the quality of both undissolved and dissolved organic matter in soil, the role of DOM as a biological indicator is still poorly understood. In this work, the fertility of 59 sites, divided into eight key alliances of the order Fagetalia sylvaticae Pawl., was studied considering chemical and biological parameters such as soil DOM, hormone-like activity, low-molecular-weight (LMW) aliphatic and phenolic acids, and floristic data. Both non-parametric tests and principal component analysis (PCA) revealed differences between silver fir and beech forests and within each type of forest. There were also differences between neutrophilous and acidophilous types. What's more, PCA reveals the dominance of the auxin (IAA)-like activity, and of some phenolic acids in distinguishing the acidophilous beeches (ACI) form the other types, whereas the gibberellin (GA)-like activity is more relevant in neutrophilous conditions such as thermophilous (THE) and mesophilous (MESO) beeches and montane (MO), high montane (HMA), high montane (HMC) silver fir forests. The GA-like activity is also related to the succinic, fumaric, malonic, and l-malic acids in the MO, HMA and HMC silver fir forests. Moreover, the role of LMW aliphatic acids in mobilizing the hormone-like activity, which improves forest growth, is stressed. The growth of seedlings of Picea abies was influenced by the phenolic acid content. At concentrations between 1 and 100 microM, phenylacetic and protocatechuic acids inhibited root growth to the same extent as indoleacetic acid, while p-hydroxybenzoic acid had a stimulating effect comparable to that of gibberellic acid. The aliphatic and phenolic acids appear to be related to plant strategies that influence soil fertility affecting plant growth through rhizodeposition. The role of LMW aliphatic and phenolic acids as molecular markers of ecosystem function is noted.     

Effects of trifluralin on soil microbial populations and the nitrogen fixation activities

Effects of trifluralin on soil microbial populations and the nitrogen fixation activity of nitrogen-fixing bacteria Azotobacter chroococcum and Bradyrhizobium japonicum and the decomposition of trifluralin by soil microorganisms were studied. Trifluralin at lower concentrations from 0.5 mg microg(-1) dry soil to lower than 10.0 mg microg(-1) dry soil appeared to stimulate the growth of soil bacteria, actinomycetes, mould, and the pure cultures of Br. japonicum and A. chroococcum. Not only the colony amounts of these two species of nitrogen-fixing bacteria increased, grown on agar medium containing lower concentrations of trifluralin, but also these colonies also enlarged in size and appeared obviously in shorter formation time. However, trifluralin at higher concentrations would inhibit the development of microbial colonies both in amount and size. Trifluralin inhibited the activity of acetylene reduction of A. chroococcum when it was added at the same time of inoculation with A. chroococcum, but it showed a noteworthy stimulation to nitrogen fixation of A.chroococcum when it was put into culture after the cells of the nitrogen-fixing bacterium had grown well. The observation that soil microorganisms could use trifluralin as sole carbon and nitrogen resources for their growth, indicated that microorganisms could decompose trifluralin well.     

Influence of sodium nitrilotriacetate (NTA) and citric acid on phenolic and organic acids in Brassica juncea grown in excess of cadmium

Brassica juncea cv. 426308 was grown in soils containing 150 mg Cd(2+)kg(-1) soil. After 38 days, the soil was amended with two rates of citric acid or NTA (10 and 20 mmol kg(-1) soil). Control soil was not amended with chelates. Plants were harvested during growth, immediately before and seven days after chelate addition. Shoot composition of organic and phenolic acids and shoot Cd(2+) concentration were determined. Cadmium concentration remained constant during the growth and increased following NTA and citric acid amendments depending on chelate type and concentration. The highest increments in Cd(2+) were measured after the addition of NTA. Compared to the control, 10 and 20 NTA-treated plants showed two- and three-fold increases, respectively. At 150 mg Cd(2+)kg(-1) soil the amount of organic and phenolic acids in the leaves of B. juncea was always higher than that detected in the control. A direct correlation between organic acid concentration and cadmium content was detected both during growth and after chelate addition. On the contrary, the amount of phenols seemed to be correlated with the metal content only in non-amended and NTA-treated plants. The 10 and 20 citric acid additions caused 45% and 90% increases in shoot phenolic acids although cadmium content rose to a smaller extent. The inhibition of citrate synthase and the entrance of phosphoenolpyruvate in shikimate pathway leading to the formation of aromatic compounds might come into play. The increase in phenylalanine ammonialyase activity following citric acid amendments suggested this metabolic response.     

Copper toxicity to Lemna minor modelled using humic acid as a surrogate for the plant root

Humic acids are chemically analogous to plant root cell walls in that their surface sites are principally comprised of carboxylic and phenolic acids which bind both metals and protons. Based on this analogy, we developed a biotic-ligand type of model to predict Cu toxicity to Lemna minor, using particulate humic acid (HA(part)) of the Windermere Humic Aqueous Model (WHAM), and 7d static-renewal exposures with five surface waters and one nutrient media which varied in DOC (1-10 mg L(-1)), pH (6.9-8.7), and water hardness (35-236 mg equivalent CaCO(3)L(-1)). Although the range of waters tested resulted in a 36-fold variation in 50% inhibitory concentration (IC50) values, the calculated concentration of Cu bound to HA(part) using this framework was highly correlated with pooled percent net root elongation (%NRE) (R(2)=0.95). Ten and fifty percent IC values based on [Cu-HA(part)] were additionally within a factor of ±1.5 and ±1.4, respectively, inclusive of 95% confidence limits. This model construct, which defines the free metal ion and the first hydrolysis product (but not metal carbonate complexes) as being bioavailable, provides an alternative means of defining the binding surface in bioavailability models, whereby a heterogeneous mixture of ligands collectively influence root-metal sorption and toxicity.     

The formation and control of disinfection by-products using chlorine dioxide

In this study, chlorine dioxide (ClO2) was used as an alternative disinfectant with vanillic acid, p-hydroxybenzoic acid, and humic acid as the organic precursors in a natural aquatic environment. The primary disinfection by-products (DBPs) formed were trihalomethanes (THMs) and haloacetic acids (HAAs). Under neutral conditions (pH = 7) for vanillic acid, more total haloacetic acids (THAAs) than total trihalomethanes (TTHMs) were found, with a substantial increase during the later stages of the reaction. In the case of p-hydroxybenzoic acid, the amount of THAAs produced was minimal. Raising the concentration of ClO2 was not favorable for the control of THAAs in low concentrations of vanillic acid. ClO2 could reduce the total amount of TTHMs and THAAs for higher concentration of vanillic acid. It was found that the humic acid treatment dosage was not significant. Under alkaline conditions (pH = 9), the control of TTHMs and THAAs for the treatment of vanillic acid was better and more economical, however, an appreciable amount of inorganic by-products were observed. Under the same alkaline condition, the control of THAA for the treatment of p-hydroxybenzoic acid was not beneficial and for the treatment of humic acid was not significant.     

Degradation of para-hydroxybenzoic acid by means of mixed microbial cultures

Olive mill wastewater contains some phenolic compounds that cause antibacterial activity of a kind that prevents biological treatment without previous dilution. Among these phenolic compounds, p-hydroxybenzoic acid (PHB) is considered to be one of the most representative. This work examines the biodegradation of PHB by aerobic microbial mixed cultures previously acclimatized to glucose, which was used as an easily biodegradable model compound. Microbial growth runs were carried out in a batch reactor in the PHB concentration range of 200-1000 mg/L. In all the runs the PHB proved to be completely degradable. The specific growth rates obtained were in the range of 0.16-0.35 l/h. Experimental runs showed that the functional relationship between the specific growth rate and PHB concentration was that proposed by Monod. The kinetic constants of the Monod equation (mu(max) and K(S)) and biomass yield coefficient (Y) were determined experimentally. With the parameter values thus obtained, a mathematical model that also takes account of the duration of the lag phase was employed to describe both the microbial growth and the consumption of PHB. The concentration values of the model fit well with the data obtained experimentally.     

Photo-Fenton treatment of water containing natural phenolic pollutants

Phenolic compounds are known to be present in high concentrations in various types of agro-industrial wastes. As they are highly biorecalcitrant, the possibility of treatment by advanced oxidation processes should be investigated. In this work, six model phenolic compounds (vanillin, protocatechuic acid, syringic acid, p-coumaric acid, gallic acid and L-tyrosine) were chosen for a demonstration of degradation by photo-Fenton reaction, under artificial light in laboratory experiments in Vienna and under sunlight in pilot-plant experiments at the Plataforma Solar de Almería in Spain. All compounds were completely mineralised. No non-degradable intermediates were produced, either in experiments with single substances or in a more complex matrix of a mixture of phenolic compounds. The expected selectivity of the photo-Fenton reaction for aromatic compounds was proven by comparison of the decrease in total organic carbon with the removal of total phenolic content.     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题,分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究,同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示,水中的有机物为腐殖酸类物质,分子量分别为1600和3500,腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳,处理前后水样DOC浓度无明显变化,而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5,经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时,DOC降至7．6mg／L,然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外,当反应初始pH值为3,过氧化氢投加量为0．5％（v／v）,亚铁和双氧水摩尔比为0．05时,出水DOC降至5．6mg／L,氧化后有小分子有机物生成。     

Degradation of phenolic and chloroaromatic compounds by Coprinus spp

Three species of Coprinus: C. sp, C. cinereus and C. micaceus were compared on solid media for some aspects of their physiological behaviour and cultural requirements (temperature, pH, substrate). Constitutive extracellular enzymatic activities were also determined. The Coprinus spp. exhibited different physiological and cultural features. Cultures of the 3 Coprinus species in synthetic liquid medium showed an efficient degradation of phenolic lignin model compounds (catechol, ferulic acid, guaiacol, phenol, protocatechuic acid syringic acid and vanillic acid) and pentachloronitrobenzene, while pentachlorophenol was not metabolized after 5 days perhaps because of a strong adsorption on mycelial biomass. It was suggested that phenoloxidases were not necessarily required for the metabolization of these compounds. Coprinus species may share a common degrading system for monomeric phenolic and chloroaromatic compounds.     

酸碱调控及底物浓度对木糖发酵产酸特性的影响

以木糖为碳源采用间歇培养方式,对木糖厌氧发酵产酸进行研究。考察木糖浓度和初始pH值对木糖厌氧产酸的影响。结果表明,随着木糖浓度的增加,总产酸量得到提高,但木糖利用率却呈现下降的趋势。当木糖浓度为5 g/L时,其利用率为100%,15 g/L时利用率为73.9%,此时挥发性脂肪酸(VFAs)为9.22 g/L。木糖的分批投加可有效促进产酸,尤其是促进乙酸浓度的提高。pH为5.0和6.0左右时,VFAs主要成分为乙酸和丁酸;而pH为7.0～9.0时,乙酸含量明显增高,在pH值为8.0的条件下乙酸含量占总VFAs的80.1%。在pH=8.0时经过8 d左右的发酵,VFAs浓度可达9.34 g/L。     

Effect of solids concentration on bacterial leaching of heavy metals from sewage sludge

Microbial metal leaching from sewage sludge (2-9% w/v) was carried out with the iron-oxidizing bacterium Thiobacillus ferrooxidans. Measurements of pH, oxidation-reduction potential, and concentration of Fe2+ indicated that T. ferrooxidans was effective in removing metals from an incubation bath containing less than 5% sludge solids concentration. Specifically, Cu leaching was completely suppressed at a high solids concentration of 9% (w/v). Results indicated that the deactivation of T. ferrooxidans at a high sludge content was mainly due to the presence of inhibiting materials such as organic matter. A mixed culture of sulfur-oxidizing bacteria was obtained by enrichment from anaerobically digested sewage sludge to enhance the efficiency of the microbial leaching process. These bacteria were much more effective in metal leaching than was iron-oxidizing T. ferrooxidans. At 9% (w/v) solids concentration, the leaching efficiencies of Zn and Cu were 78% (2.66 g/kg dry sludge) and 59% (1.36 g/kg dry sludge), respectively. Therefore, when removing heavy metals from the anaerobically digested sewage sludge, the indigenous sulfur-oxidizing bacteria isolated in the current study were more efficient than T. ferrooxidans, especially at high sludge solids concentrations.     

生化黄腐酸对污染水体生物修复的强化作用

研究了生化黄腐酸（BFA）对污染水体生物修复的强化作用。生化黄腐酸能提高水体中微生物活性,加快微生物对目标污染物的降解。在污染水体生物修复强化作用的试验中,投加生化黄腐酸,CODCr、NH3-N、TP和浊度的去除率分别增加了29．47％、20．61％、35％和19．86％,同时有利于水体DO的提升。     

Dicarboxylic acid concentration trends and sampling artifacts

Dicarboxylic acids associated with airborne particulate matter were measured during a summer period in Philadelphia that included multiple air pollution episodes. Samples were collected for two 10 h periods each day using a high-volume sampler with two quartz fiber filters in series, and analyzed by gas chromatography mass spectrometry (GCMS) with diazomethane derivatization. Among the dicarboxylic acids investigated, phthalic acid and adipic acid exhibited the greatest diurnal variations and the strongest linear relationship with maximum daily ozone concentration. Dicarboxylic acids and ozone concentration exhibited a poor linear relationship with organic to elemental carbon ratio. All species investigated were affected by significant sampling artifact errors at low concentrations, but sampling errors were negligible at high concentrations observed during ozone episodes.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Biodegradation of aromatic hydrocarbons by Haloarchaea and their use for the reduction of the chemical oxygen demand of hypersaline petroleum produced water

Ten halophilic Archaea (Haloarchaea) strains able to degrade aromatic compounds were isolated from five hypersaline locations; salt marshes in the Uyuni salt flats in Bolivia, crystallizer ponds in Chile and Cabo Rojo (Puerto Rico), and sabkhas (salt flats) in the Persian Gulf (Saudi Arabia) and the Dead Sea (Israel and Jordan). Phylogenetic identification of the isolates was determined by 16S rRNA gene sequence analysis. The isolated Haloarchaea strains were able to grow on a mixture of benzoic acid, p-hydroxybenzoic acid, and salicylic acid (1.5 mM each) and a mixture of the polycyclic aromatic hydrocarbons, naphthalene, anthracene, phenanthrene, pyrene and benzo[a]anthracene (0.3 mM each). Evaluation of the extent of degradation of the mixed aromatic hydrocarbons demonstrated that the isolates could degrade these compounds in hypersaline media containing 20% NaCl. The strains were shown to reduce the COD of hypersaline crude oil reservoir produced waters significantly beyond that achieved using standard hydrogen peroxide treatment alone.     

Characterization and microbial utilization of dissolved organic carbon in groundwater contaminated with chlorophenols

The aim of this study was to characterize the labile part of dissolved organic carbon (DOC) present in groundwater by identification of natural organic carbon substrates and to assess their microbial utilization during aeration of the groundwater. The studied chlorophenol (CP) contaminated groundwater contained 60-2650 micromoll(-1) of DOC of which up to 98.0% were CPs; 1.7% were low-molecular weight organic acids and 0.2% were dissolved free amino acids. Traces of following natural organic carbon substrates were identified: L-alanine, L-isoleucine, L-leucine, L-serine, L-threonine, L-tyrosine, L-valine, L-aspartic, acetic, citric, formic, lactic, malic and oxalic acid. Dissolved oxygen concentration inside the CP-plume was lower (mean 25 micromoll(-1)) than outside of the plume (mean 102 micromoll(-1)). Over a monitoring period of four years the concentrations of CPs, Fe(II) and NH4+ were higher inside than outside of the CP-plume. Oxygen availability within the CP-plume limits in situ biological oxidation of CPs, DOC, NH4+ and Fe(II). The microbial enzymatic hydrolysis rates of 4-methylumbelliferyl and 7-amino-4-methylcoumarin-linked substrates varied from 0.01 to 52 micromoll(-1)h(-1) and was slightly higher inside than outside the plume. Microbial uptake rates of 14C-acetate, 14C-glucose and 14C-leucine were on average 28, 4 and 4 pmoll(-1)h(-1) outside and 17, 25 and 8 pmoll(-1)h(-1) inside the plume, respectively. The indigenous microorganisms were shown able of hydrolysis of dissolved organic matter, uptake and utilization of natural organic carbon substrates. Therefore, the labile part of DOC serves as a pool of secondary substrates beside the CP-contaminants in the groundwater and possibly help in sustaining the growth of CP-degrading bacteria.     

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.     

Characterization of bacterial diversity in an atrazine degrading enrichment culture and degradation of atrazine,cyanuric acid and biuret in industrial wastewater

An enrichment culture was used to study atrazine degradation in mineral salt medium (MSM) (T1), MSM+soil extract (1:1, v/v) (T2) and soil extract (T3). Results suggested that enrichment culture required soil extract to degrade atrazine, as after second sequential transfer only partial atrazine degradation was observed in T1 treatment while atrazine was completely degraded in T2 and T3 treatments even after fourth transfer. Culture independent polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) technique confirmed selective enrichment of genus Bacillus along with Pseudomonas and Burkholderia. Degradation of atrazine/metabolites in the industrial wastewater was studied at different initial concentrations of the contaminants [wastewater-water (v/v) ratio: T1, 1:9; T2, 2:8; T3, 3:7; T4, 5:5 and T5, undiluted effluent]. The initial concentrations of atrazine, cyanuric acid and biuret ranged between 5.32 and 53.92 µg mL^?1, 265.6 and 1805.2 µg mL^?1 and 1.85 and 16.12 µg mL^?1, respectively. The enrichment culture was able to completely degrade atrazine, cyanuric acid and biuret up to T4 treatment, while no appreciable degradation of contaminants was observed in the undiluted effluent (T5). Inability of enrichment culture to degrade atrazine/metabolites might be due to high concentrations of cyanuric acid. Therefore, a separate study on cyanuric acid degradation suggested: (i) no appreciable cyanuric acid degradation with accumulation of an unidentified metabolite in the medium where cyanuric acid was supplemented as the sole source of carbon and nitrogen; (ii) partial cyanuric acid degradation with accumulation of unidentified metabolite in the medium containing additional nitrogen source; and (iii) complete cyanuric acid degradation in the medium supplemented with an additional carbon source. This unidentified metabolite observed during cyanuric acid degradation and also detected in the enrichment culture inoculated wastewater samples, however, was degraded up to T4 treatments and was persistent in the T5 treatment. Probably, accumulation of this metabolite inhibited atrazine/cyanuric acid degradation by the enrichment culture in undiluted wastewater.     

Effect of Solids Concentration on Bacterial Leaching of Heavy Metals from Sewage Sludge

Abstract

Microbial metal leaching from sewage sludge (2-9% w/v) was carried out with the iron-oxidizing bacterium Thiobacillus ferrooxidans. Measurements of pH, oxidation-reduction potential, and concentration of Fe²⁺ indicated that T. ferrooxidans was effective in removing metals from an incubation bath containing less than 5% sludge solids concentration. Specifically, Cu leaching was completely suppressed at a high solids concentration of 9% (w/v). Results indicated that the deactivation of T. ferrooxidans at a high sludge content was mainly due to the presence of inhibiting materials such as organic matter. A mixed culture of sulfur-oxidizing bacteria was obtained by enrichment from anaerobically digested sewage sludge to enhance the efficiency of the microbial leaching process. These bacteria were much more effective in metal leaching than was iron-oxidizing T. ferrooxidans. At 9% (w/v) solids concentration, the leaching efficiencies of Zn and Cu were 78% (2.66 g/kg dry sludge) and 59% (1.36 g/kg dry sludge), respectively. Therefore, when removing heavy metals from the anaerobically digested sewage sludge, the indigenous sulfur-oxidizing bacteria isolated in the current study were more efficient than T. ferrooxidans, especially at high sludge solids concentrations.