废水中硝基酚类化合物生物降解的研究进展

硝基酚是一类重要且常用的化工原料，一些硝基酚毒性大且难以生物降解，被美国环保局列入“优先控制污染物名单”。在自然环境条件下，硝基酚的生物降解速率缓慢，导致硝基酚在环境中长期滞留和积累。分析了人工强化条件下废水中硝基酚的生物降解性能，主要从具有降解硝基酚能力的微生物、硝基酚的厌氧生物降解性、硝基酚的好氧生物降解性和硝基酚的共基质代谢降解方面进行了较全面的综述，讨论了该研究当前仍存在的一些问题和研究展望。     

Measurement of phase-distributed nitrophenols in Rome ambient air

Atmospheric nitrophenols (NPs) were determined both in the gas and particle phases by combining the annular denuder sampling technique with GC-MS analysis. The phase distribution of six mono-NPs identified in air sampled in downtown Rome was assessed. 4-NP, 3-methyl-4-NP and 2,6-dimethyl-4-NP were found for more than 75% in the particle phase, whilst 2-NP, 4-methyl-2-NP and 5-methyl-2-NP predominated in the gas phase. Concentration levels lower than 20 ng m-3 were observed for all NPs, among which 4-NP (17.8+/-5.6 ng m-3) and 2-NP (10.4+/-4.2 ng m-3) were the most abundant congeners in the two phases, respectively.     

Phenol and nitrophenols in the air and dew waters of Santiago de Chile

Phenol, nitrophenols and dinitrophenols were measured in air and dews in downtown Santiago de Chile. In both systems, phenol, 2-nitrophenol (2-NP), and 4-nitrophenol (4-NP) were the compounds found in higher concentrations and with major frequency. Temporal profiles in air were compatible with a significant direct incorporation from mobile sources. The data can be explained in terms of a faster removal of 2-NP than 4-NP, with the former predominating in fresh air masses and 4-NP in more aged samples. All these compounds, as well as dinitrophenols, were found in dew waters. Simultaneous measurements in air and dew indicate that phenol present in dew exceeds that expected in equilibrated samples, while the opposite occurs with 4-NP. This last result is associated to mass transfer limitations for the highly water soluble nitroderivative.     

Increased concentrations of nitrophenols in leaves from a damaged forestal site

A class of organic micropollutants, the phytotoxic nitrophenols, were analysed in the vegetation (beech leaves), from two different alpine sites (Val Gerola and Val Masino) in the Lombardy Region (Northern Italy), using gas chromatography-mass spectrometry.Leaves from the more damaged site (Val Gerola) had higher mean total nitrophenol concentrations (313 ng/g) than the Val Masino samples (148 ng/g). Since the dinitrophenol levels in leaves are close to the concentrations exerting a phytotoxic effect in vitro, these pollutants presumably have an active role in the symptoms of tree diseases in these alpine sites.     

Influence of pH on the toxicity of nitrophenols to Microtox and Spirotox tests

The toxicity of mononitrophenols and dinitrophenols (DNP) to luminescent bacteria Vibrio fischeri (Microtox test) and ciliated protozoan Spirostomum ambiguum (Spirotox test) was evaluated. Spirotox was more sensitive to the tested nitrophenols (NPs) than the Microtox test. 2,5-DNP was the most toxic and 2-NP was the least toxic to the both bioindicators. The toxicity depended greatly on the pH of the medium. The highest changes were observed for DNPs, where the toxicity decreased more than 20-times when the pH increased from 6 to 8. No significant decrease of the toxicity was found for NPs, when the pH increased from 6 to 7. Greater increase of the pH to 8 caused from 1.5 to 4-fold decrease of the toxicity.     

以有机酸为共基质硝基酚厌氧生物降解性研究

在中温厌氧消化条件下 ,以有机酸 (乙酸与丙酸的混合酸 )为共基质 ,通过测定甲烷累积产量 ,研究了 2 硝基酚、2 ,4 二硝基酚的厌氧生物降解性。试验条件为 :温度 35℃ ,COD 110 0～ 12 0 0mg/L ,pH 7 0～ 7 5 ,COD/VSS为 0 1,接种污泥未驯化 ,其产甲烷活性CH4/VSS为 195mL/g。研究结果表明 ,在所选的浓度范围内 (≤ 4 4mg/L) ,2 硝基酚对产甲烷过程没有产生抑制作用 ;2 ,4 二硝基酚是抑制性较强的物质 ,浓度为 12～ 2 0mg/L时产生中度抑制 ,大于 2 8mg/L时产生重度抑制     

纳米TiO_2光催化降解硝基酚类污染物动力学及机理的研究

采用纳米TiO2(P25)粉末作为催化剂,研究了几种典型硝基取代酚在TiO2/UV悬浮体系下的光催化降解.研究表明,这些化合物的降解过程符合Langmuir-Hinshelwood动力学方程,其表观速率常数(kapp)的大小为:2-氨基-4硝基酚(2-A,4-NP)>4-硝基酚(4-NP)>2-硝基酚(2-NP)>3-硝基酚(3-NP)>2,4-二硝基酚(2,4-DNP)>2,4,6-三硝基酚(2,4,6-TNP),而吸附平衡常数(KL)却与Kapp成反比.苯环上取代基的种类和数日对有机物光催化降解活性有很大的影响,硝基的加入降低了光催化活性,并且kapp与Hammett常数(σ)具有较好的线性关系.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

Hydrogen peroxide photolysis, fenton reagent and photo-fenton for the degradation of nitrophenols: a comparative study

The kinetics of the degradation of seven nitrophenols (2-nitrophenol, 4-nitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, 2-methyl-4,6-dinitrophenol, 4-methyl-2,6-dinitrophenol) with the Fenton reagent, photo-Fenton, and hydrogen peroxide photolysis was investigated. The efficiency and operating costs for the studied treatments were evaluated and compared. The Fenton reagent was found to be the most efficient and the cheapest way for the nitrophenols (NPs) degradation. The formation of nitrate as a result of mineralisation of organically bounded nitrogen was observed during the treatment of NPs with studied treatment processes. The degrees of organically bounded nitrogen conversion to nitrate after 90% degradation of NPs with the Fenton, photo-Fenton and hydrogen peroxide photolysis were 51-67%, 85-90%, and 50-60%, respectively. According to Daphnia magna acute toxicity test, the Fenton treatment led to complete detoxification of NPs.     

纳米TiO2光催化降解硝基酚类污染物动力学及机理的研究

采用纳米TiO₂(P25)粉末作为催化剂,研究了几种典型硝基取代酚在TiO₂/UV悬浮体系下的光催化降解。研究表明，这些化合物的降解过程符合Langmuir-Hinshelwood动力学方程，其表观速率常数(k_app)的大小为：2-氨基-4硝基酚（2-A,4-NP）＞4-硝基酚（4-NP）＞2-硝基酚（2-NP）＞3-硝基酚（3-NP）＞2,4-二硝基酚（2,4-DNP）＞2,4,6-三硝基酚（2,4,6-TNP），而吸附平衡常数(KL)却与k_app成反比。苯环上取代基的种类和数目对有机物光催化降解活性有很大的影响，硝基的加入降低了光催化活性，并且k_app与Hammett常数（σ）具有较好的线性关系。     

Formation of nitrophenols upon UV irradiation of phenol and nitrate in aqueous solutions and in TiO2 aqueous suspensions.

The formation of nitrophenols was studied as a consequence of ultra violet (UV) irradiation of aqueous solutions of phenol and nitrate in the range of pH 1-12. The study was performed both in homogeneous phase and in the presence of water-suspended TiO2. The effects of pH, dissolved oxygen and 2-propanol as .OH scavenger have been evaluated. A reaction mechanism is proposed, based on the experimental results.     

Wet deposition of pesticides and nitrophenols at two sites in Denmark: measurements and contributions from regional sources

The concentrations of selected pesticides, of some of their degradation products and nitrophenols in rain were measured at two stations in Denmark in the period January 2000-July 2001. Forty compounds were quantified at least at one station during at least one sampling period. Additionally 17 compounds could be detected but not quantified, and 22 compounds could not be detected at all. The highest depositions of pesticides were observed for pendimethalin and desethylterbuthylazine, which is a degradation product of terbuthylazine. The deposition of the nitrophenols 2,4-dinitrophenol, DNOC, 3-methyl-4-nitrophenol was much higher than that of pesticides. The deposition of 2,4-dinitrophenol was e.g. up to a factor of 40 higher than that of pendimethalin. Atrazine, chloridazon, 2,4-D, dieldrin, disulfoton, fenitrothion, isoproturon, lenacil, metazachlor and propachlor were found in precipitation, although these pesticides are not allowed in Denmark. It can therefore be concluded that they came from abroad and have been transported over at least 60-80 km. For some of these compounds the transport distance is much longer.     

Nitrated monoaromatic hydrocarbons (nitrophenols,nitrocatechols, nitrosalicylic acids) in ambient air: levels,mass size distributions and inhalation bioaccessibility

Environmental Science and Pollution Research - Nitrated monoaromatic hydrocarbons (NMAHs) are ubiquitous in the environment and an important part of atmospheric humic-like substances (HULIS) and...     

Determining the role of humic substances in the fate of pesticides in the environment

Abstract

The data presented in this paper emphasize that the behavior and fate of pesticides in the environment is influenced by humic substances. Various methods most frequently used for the characterization of humic substances are discussed. Both humic acid and fulvic acid can solubilize in water certain organic compounds and are important carriers of some pesticides in soil. Humic substances have the potential for promoting the nonbiological degradation of many pesticides. Several methods of bleaching humus color from drinking water, including chlorination, ozonation, and UV‐radiation, are described. Finally, the photochemical stability to UV‐radiation of certain pesticides in aqueous fulvic acid solution is discussed.     

Determining the role of human substances in the fate of pesticides in the environment

The data presented in this paper emphasize that the behavior and fate of pesticides in the environment is influenced by humic substances. Various methods most frequently used for the characterization of humic substances are discussed. Both humic acid and fulvic acid can solubilize in water certain organic compounds and are important carriers of some pesticides in soil. Humic substances have the potential for promoting the nonbiological degradation of many pesticides. Several methods of bleaching humus color from drinking water, including chlorination, ozonation, and UV-radiation, are described. Finally, the photochemical stability to UV-radiation of certain pesticides in aqueous fulvic acid solution is discussed.     

An assessment of the aggregate impacts of the proposed reduction in the motor fuels tax in the United States

The analysis in this paper examines the impact of reducing the excise tax on gasoline and diesel fuel on the United States economy. The analytical approach used consists of a computable general equilibrium model composed of fourteen producing sectors, fourteen consuming sectors, six household categories classified by income and the government. The effects of a 4.3 cents per gallon reduction in the excise tax on gasoline and diesel fuel on prices and quantities are examined. The results suggest, for example, that a decrease in the tax would result in higher output by the producing sectors (by about $2.86 billion), and expansion in the consumption of goods and services (by about $3.48 billion), and an increase in welfare (by about $3.59 billion). The government would realise a decrease in revenue of about $2.37 billion. When subjected to a sensitivity analysis, the results are reasonably robust with regard to the assumption of the values of the substitution elasticities.