Photochemical behavior of parathion in the presence of humic acids from different origins

This paper reports the effect of ultraviolet radiation on the degradation of pesticide ethyl parathion in the presence of humic acids. Ethyl parathion was completely degraded in 300 min using an artificial lamp of 7.41 x 10(-10) einstein/s. Humic acid from peat did not influence the photochemical rate (k = 8.92 x 10(-3) min). However, in the presence of aquatic humic acid, the photochemical rate was higher (11.5 x 10(-3) min). The analytical determinations show the presence of p-nitrophenol and aminophenol in the reaction medium during the photochemical experiments. The kinetic of degradation in all experiments obeyed a first-order reaction pattern.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Characterization of the humic material formed by composting of domestic and industrial biowastes Part 1. HPLC of the cupric oxide oxidation products from humic acids

The changes induced by humification of anaerobically digested sewage sludge, source separated biowaste, and pulp mill biosludge were determined by extracting the fractions of bitumen and humic and fulvic acids from the samples of fresh and humified composts. In all cases, a distinct decrease in the amount of bitumen could be detected during humification. The amount of humic acids increased in sewage sludge and biowaste samples, but decreased in pulp mill biosludge sample during humification. The humic acids were degraded by CuO oxidation and the phenolic degradation products were analysed by reversed-phase high-performance liquid chromatography. The yield of these aromatic degradation products was in the range 0.9–2.0 % for each sample. The main phenolic degradation products were 4-hydroxybenzoic acid, vanillic acid, 4-hydroxybenzaldehyde, vanillin, syringaldehyde, and acetovanillone. Two lignin dimers, dehydrodivanillin and dehydrodiacetovanillone, were also identified.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl(-) increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl(-) at total mineralization was detected when initial diuron concentration was 13.8 mg L(-1). For N species, the final concentrations of NO3(-) and NH4+ after 60 min of reaction time were 0.28 and 0.19 mg L(-1), respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na2CO3, additive NaHCO3 and additive H2O2 were all advantageous to improve the degradation efficiency of diuron.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl^? increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl^? at total mineralization was detected when initial diuron concentration was 13.8 mg L^?1. For N species, the final concentrations of NO₃ ^? and NH₄ ⁺ after 60 min of reaction time were 0.28 and 0.19 mg L^?1, respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na₂CO₃, additive NaHCO₃ and additive H₂O₂ were all advantageous to improve the degradation efficiency of diuron.     

Decomposition of phorate in aqueous solution by ozonation

Phorate (O,O-diethyl S-ethylthiomethyl phosphorodithioate) dissolved in aqueous solution was almost completely decomposed by ozonation to form various species within 10 minutes of reaction time for the experimental conditions examined in this research. The generation rate of sulfate was found to be fairly independent of solution pH value. However, the formation of phosphate and carbonate was more favorable for alkaline solutions where hydroxyl free radical is the primary oxidative species. The reaction rates increased with initial gaseous ozone concentrations, indicating the reaction was mass transfer-controlled within the experimental range of this research. Combining the analytical results by various instruments, including gas chromatograph equipped with an electron ionization detector (GC-EID), high performance liquid chromatography (HPLC), ion chromatography (IC), and total organic carbon (TOC), the temporal sequence of phorate ozonation was proposed in this study. The oxidation of sulfur atoms on the phosphorus-sulfur double bond or carbon-sulfur-carbon bond by ozonation was found to occur at first to form sulfate and various intermediates.     

Fluorescence fingerprint of fulvic and humic acids from varied origins as viewed by single-scan and excitation/emission matrix techniques

Excitation/emission matrix (EEM), single-scan excitation and synchronous fluorescence spectra of a series of FA and HA from distinct environments are presented. The EEM plots show at least four spectral features whose corresponding Ex/Em pairs relate to the alpha', alpha, beta and gamma (or delta) fluorophores previously found in natural waters spectra. The alpha' and alpha peaks, which identify typical humic-like components, are present in all samples, independently of the organic matter (OM) source. In FA, their Ex/Em pairs are approximately 260 nm/460 nm and approximately 310 nm/440 nm, respectively. In HA their excitation and emission maxima are red-shifted, the corresponding Ex/Em pairs being located at approximately 265 nm/525 nm and approximately 360 nm/520 nm, respectively. The appearance of beta and gamma (or delta) peaks is dependent both on the OM origin and on HS aging. The former (Ex/Em approximately 320 nm/430 nm), that has been associated with the incidence of marine humic-like material, is present only in a few marine and estuarine HA. It emerges as a shoulder on the alpha peak and its detection is dependent on a balance between its magnitude and the magnitude and emission maxima location of the alpha peak. The gamma (or delta) peak (Ex/Em approximately 275 nm/315 nm in FA, and approximately 275 nm/330 nm in HA), on the other hand, is better visualized in FA than in HA diagrams. It has typical protein-, mainly tryptophan-like, fluorescence properties and appears with varied significance in a few marine and estuarine samples being hardly detected in samples from exclusively terrestrial environments. It is also shown in this study that with selected lambda(ex), lambda(em) and (delta)(lambda) values, regular emission, excitation and synchronous spectra can, together, provide a good picture of the OM sources and aging for extracted HS.     

Decomposition of 2-mercaptothiazoline in aqueous solution by ozonation

This study investigates the ozonation of 2-mercaptothiazoline (2-MT). The 2-MT is one of the important organic additives for the electroplating solution of the printed wiring board industry and has been widely used as a corrosion inhibitor in many industrial processes. It is of concern for the aquatic pollution control especially in the wastewaters. Semibatch ozonation experiments in the completely stirred tank reactor are performed under various concentrations of input ozone. The concentrations of 2-MT, sulfate, and ammonium are analyzed at specified time intervals to elucidate the decomposition of 2-MT during the ozonation. In addition, the time variation of the dissolved ozone concentration (C(ALb)) is continuously monitored in the course of experiments. Total organic carbon (TOC) is chosen and measured as a mineralization index of the ozonation of 2-MT. The results indicate that the decomposition of 2-MT is efficient, while the mineralization of TOC is limited via the ozonation only. Simultaneously, the yield of sulfate with the maximum value of about 47% is characterized by the increases of TOC removal and ozone consumption. These results can provide some useful information for assessing the feasibility of the treatment of 2-MT in the aqueous solution by the ozonation.     

Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

Equilibrium sorption of phenanthrene by soil humic acids

This study investigated the effect of chemical heterogeneity of humic acids (HAs) on the equilibrium sorption of phenanthrene by HA extracts. Six HA samples were extracted from three different soils with 0.5 M NaOH and 0.1 M Na₄P₂O₇ and were characterized with elemental analysis, infrared spectrometry, and solid-state ¹³C nuclear magnetic resonance (NMR) spectrometry. The equilibrium sorption measurements were carried out with a batch technique and using the six HA solids as the sorbents and phenanthrene as the sorbate. The measured sorption isotherm data were fitted to the Freundlich equation. The results showed that, for the same soil, (i) the total HA mass extracted with Na₄P₂O₇ was 13.7–22.6% less than that extracted with NaOH, (ii) the Na₄P₂O₇-extracted HA had higher O/C atomic ratio, greater content of polar organic carbons (POC), and lower aliphatic carbon content than the NaOH-extracted HA, and (iii) the Na₄P₂O₇-extracted HA exhibited greater sorption isotherm linearity and but not dramatic difference in sorption capacities than the NaOH extracted HA. The differences in the HA properties resulting from the two different extraction methods may be because NaOH can hydrolyze insoluble HA fractions such as fatty acid like macromolecules bound on soils whereas Na₄P₂O₇ could not. As a result, the HAs extracted with the two different methods had different polarity and functionality which affected their sorption property for phenanthrene.     

腐植酸强化苯酚厌氧发酵降解

在无外加电子受体的条件下,首次研究了腐植酸对活性污泥厌氧降解苯酚的影响。研究结果表明,腐植酸Suwannee River Humic Acid Standard(SR-HA)、Leonardite Humic Acid Standard(L-HA)和Pahokee Peat Humic Acid(PP-HA)作为氧化还原介体能够提高苯酚的厌氧发酵降解效率。其中腐植酸PP-HA对苯酚的厌氧降解表现出了最为明显的强化效果,反应进行36 h后,苯酚去除率提高了18.5%。当单独投加的PP-HA浓度在0至100 mg/L范围内,苯酚的厌氧降解效率随着腐植酸浓度增加而逐渐提高,而浓度大于100 mg/L后,腐植酸对苯酚降解效率的促进作用随着PP-HA浓度的增加逐渐减缓。除此之外,当低浓度的蒽醌-2-磺酸钠(AQS)(0.02 mM)和PP-HA(20 mg/L)在反应体系中共存时,相比于无介体存在的对照组,苯酚厌氧降解效率提高了约1.4倍。产物分析结果表明,乙酸和CH4作为苯酚发酵降解的重要产物被检测出来。最后,在氧化还原介体腐植酸的存在下,初步探讨了苯酚厌氧发酵降解的代谢途径。     

Fluorescence behaviour of Zn and Ni complexes of humic acids from different sources

Conventional fluorescence spectroscopy in the excitation, emission and synchronous scan modes and three-dimensional fluorescence spectroscopy in the form of an excitation-emission matrix (EEM) of fluorescence intensity as a function of excitation and emission wavelengths have been applied to the study of three humic acids (HAs) extracted from soil (SHA), peat (PHA) and compost (CHA) and their interaction products with Zn(II) and Ni(II) ions. Fluorescence spectra of HAs appear to be related to the nature and origin of the sample. A strong reduction of intensity of all peaks is observed in the spectra of HAs-metal complexes as compared to those of untreated HAs. Ni(II) exhibits greater quenching ability than Zn(II). Fluorescence quenching measured for complexes of HAs at increasing Ni(II) concentrations was linearly correlated with metal ion concentration. The different capacity to interact with metal ions showed by various HAs is attributed to their different molecular complexity.     

不同来源溶解态腐殖酸与Cu2+作用的荧光特性

利用三维荧光等高线图以及其所确定的荧光峰荧光强度随溶液化学条件的变化,研究不同来源溶解态腐殖酸与Cu²⁺作用的荧光特性。研究结果表明：溶解态天然腐殖酸中主要存在二类发射荧光的有机物官能团能与Cu²⁺发生络合作用。位于激发波长和发射波长分别为271～281 nm和335～351 nm的荧光峰1所代表的有机物官能团是与Cu²⁺发生络合配位的主要点位;pH值为4～6时,其络合受pH值影响较显著;而受溶液离子强度影响较小。位于激发波长和发射波长分别为223～246 nm和335～371 nm的荧光峰2所代表的有机物官能团与Cu²⁺的络合作用受溶液pH值影响较小,受溶液离子强度影响较显著。溶解态商品腐殖酸荧光峰1′所代表的有机物官能团与Cu²⁺的络合作用荧光特性,与天然腐殖酸荧光峰1所代表的有机物官能团和Cu²⁺络合作用荧光特性相似,在pH值为3～7时,其络合受pH值影响较显著。     

Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.     

臭氧光催化降解水中甲醛的研究

研究比较了3种光化学方法对水中低浓度甲醛的降解效果,考察了初始pH值、甲醛浓度和臭氧投加速率等因素对臭氧光催化(TiO_2/UV/O_3)降解甲醛的影响。结果表明,紫外臭氧(UV/O_3)、光催化(TiO_2/UV)和TiO_2/UV/O_3对甲醛的降解均符合表观一级反应动力学,TiO_2/UV/O_3降解甲醛的一级表观速率常数大于TiO_2/UV与UV/O_3之和,说明臭氧、光催化有明显的协同作用。pH值对臭氧光催化降解甲醛的速率几乎没有影响;甲醛初始浓度增加,表观反应速率常数下降,但甲醛的绝对去除量仍随初始浓度的增加而显著增加;臭氧投加速率增加,降解速率增加。甲醛降解的主要中间产物为甲酸,但甲酸在臭氧光催化反应过程中也快速降解而被矿化,说明臭氧光催化是一种能安全有效去除甲醛的方法。     

天然锰矿催化臭氧氧化降解水中4-氯酚的研究

以天然锰矿为金属催化剂,研究了锰矿催化臭氧氧化水中4-氯酚的降解效果。采用毛细管电泳方法及色质联用技术．分别对反应的中间产物和终产物进行了分析。推测了锰矿催化臭氧氧化水中4-氯酚的降解反应机理可能为：锰矿的吸附氧化与锰矿生成的Mn^2 催化臭氧分解．产生更多高活性的羟基自由基．从而提高了臭氧的氧化能力。     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

Evaluation of photolysis and hydrolysis of atrazine and its first degradation products in the presence of humic acids

Relative importance of hydrolysis and photolysis of atrazine and its degradation products in aqueous solutions with dissolved humic acids (HA) has been assessed under exposure to sunlight and under UV irradiation. Quantum yield for direct photolysis of atrazine at 254 nm was 0.037 mol photon(-1), the reaction order was 0.8. Atrazine, desethylatrazine and desisopropylatrazine converted to their 2-hydroxy analogs with rate constants 0.02-0.08 min(-1) in clear solutions, while addition of HA (300 mg L(-1)) caused a 10-fold increase in rate constants. Hydroxyatrazine was not degraded. No evidence of photo-Fenton reaction was found. Under exposure to solar light, atrazine, desethylatrazine and desisopropylatrazine were converted to 2-hydroxy analogs only at pH 2 because of acid hydrolysis and possible contribution of photolysis. At lower HA concentration, only their light-shielding effect was noticed, while at higher concentrations, HA-catalysed hydrolysis prevailed. Hydroxyatrazine concentration diminished at all pH values in solutions without HA exposed to sunlight.     

Fe and UV-enhanced ozonation of chlorophenolic compounds in aqueous medium

Mono-, di- and trichlorophenol including different isomers were degraded by O₃, O₃ + UV and O₃ + UV + Fe³⁺. Disappearance rates are nearly identical among three ozonations. Whereas TOC elimination was not completed by ozone alone. UV illumination accelerated TOC elimination rate and the addition of Fe³⁺ (O₃ + UV + Fe³⁺) further accelerated it. TOC elimination rates among different chlorophenols were in the order of mono > di > tri. The effect of Fe³⁺ was largest on the degradation of trichlorophenol. Hydroxylated aromatics, organic acids, formaldehyde and acetone were detected as intermediates.     

Comparison of advanced oxidation processes and identification of monuron photodegradation products in aqueous solution

The photodegradation of monuron (3-(4-chlorophenyl)-1,1-dimethylurea) in aqueous solutions under simulated solar irradiation has been conducted by different advanced oxidation processes (UV/H(2)O(2), UV/H(2)O(2)/Fe(2+), UV/H(2)O(2)/TiO(2), UV/TiO(2), dark H(2)O(2)/Fe(3+)). The degradation rates were always higher for the homogeneous catalysis in photo-Fenton reactions (UV/H(2)O(2)/Fe(2+)) compared to the heterogeneous photocatalytic systems (TiO(2)/UV and UV/H(2)O(2)/TiO(2)). Optimal concentrations of Fe(2+) and H(2)O(2) for the abatement of the herbicide in the photo-Fenton system were found to be 1 mM Fe(II) and 10 mM H(2)O(2). Several intermediary products were identified using large volume injection micro-liquid chromatography with UV detection (mu-LC-UV), mu-LC-MS and GC-MS techniques and a degradation mechanism has been proposed.