Uptake and localization of gaseous phenol and p-cresol in plant leaves

Understanding foliar uptake processes for organic air pollutants is critical to predicting the fate of these compounds, including their entry into the food chain and their susceptibility to plant-, microbe-, and light-mediated degradation. We characterized the uptake kinetics for gaseous phenol and p-cresol into the leaves of maize seedlings in a closed system over periods up to 23h. When leaves were exposed to mixtures of phenol and p-cresol (3-50microg l(-1) each), the air concentrations of the compounds rapidly decreased, showing residence times of 4-6h. The stomata of the leaves were mostly or completely closed, suggesting that uptake was primarily through the cuticle. The involvement of a cuticular uptake pathway was confirmed based on increased uptake into two cuticular mutants of maize. Models of the uptake data suggested that, at the concentrations used, phenol and p-cresol were taken up in a biphasic manner, consistent with previous two-compartment models for foliar uptake of lipophilic compounds via a cuticular pathway. These models also indicated that phenol was taken up at a slightly faster rate than p-cresol. To begin to understand the fate of these compounds, we examined the location of (14)C in leaves exposed to (14)C-phenol. Significantly more (14)C accumulated in the terminal centimeter than in the central and basal regions of the leaves on both a mass and area basis. This is the first demonstration that a gaseous organic compound, or its breakdown products, accumulates in a spatially non-uniform manner in leaves following foliar uptake. These findings support a role for plants as natural, or deliberate, attenuators of airborne pollutants, and suggest potential availability of these compounds to the leaf surface microflora.     

Comparison of seasonal phenol and p-cresol emissions from ground-level area sources in a dairy operation in central Texas

Although there are more than 200 odor-causing volatile organic compounds (VOCs), phenol and p-cresol are two prominent odor-causing VOCs found downwind from concentrated animal feeding operations (CAFOs). The VOC emissions from cattle and dairy production are difficult to quantify accurately because of their low concentrations, spatial variability, and limitations of available instruments. To quantify VOCs, a protocol following US. Environmental Protection Agency (EPA) Method TO-14A has been established based on the isolation flux chamber method and a portable gas chromatograph (GC) coupled with a purge-and-trap system. The general objective of this research was to quantify phenol and p-cresol emission rates (ERs) from different ground-level area sources (GLASs) in a free-stall dairy during summer and winter seasons using this protocol. Two-week-long sampling campaigns were conducted in a dairy operation in central Texas. Twenty-nine air samples were collected during winter and 37 samples were collected during summer from six specifically delineated GLASs (barn, loafing pen, lagoon, settling basin, silage pile, and walkway) at the free-stall dairy. Thirteen VOCs were identified during the sampling period and the GC was calibrated for phenol and p-cresol, the primary odorous VOCs identified. The overall calculated ERs for phenol and p-cresol were 2656 +/- 728 and 763 +/- 212 mg hd(-1) day(-1), respectively, during winter. Overall phenol and p-cresol ERs were calculated to be 1183 +/- 361 and 551 +/- 214 mg hd(-1) day(-1), respectively, during summer. In general, overall phenol and p-cresol ERs during winter were about 2.3 and 1.4 times, respectively, higher than those during summer.     

酚类化合物在2-羧基苯甲酰基修饰的超高交联树脂上的吸附

合成了一种用来吸附和去除水溶液中酚类化合物的 2 羧基苯甲酰基修饰的超高交联吸附树脂 (ZH 0 1) ,并从动力学和吸附容量角度比较了XAD 4、AM 1和ZH 0 1分别吸附浓度为 80 0mg/L苯酚的情况。实验结果表明 ,ZH 0 1吸附剂有利于吸附苯酚、对甲苯酚和对硝基苯酚之类的酚类化合物。动力学和热力学研究都得到了相同的结果 :ZH 0 1对苯酚和对甲苯酚吸附是化学吸附的过渡状态 ,而对对硝基苯酚的吸附是一种物理吸附过程 ,并且显示了ZH 0 1表面均孔特性。苯酚在ZH 0 1上的小柱吸附研究表明了吸附穿透容量和总吸附量分别为 2 .38mmol/g和 3.0 5mmol/g ,溶剂甲醇对吸附在ZH 0 1上苯酚的脱附效果较好。     

含氮芳香化合物的厌氧生物降解研究回顾

回顾了硝基芳香化合物和偶氮化合物在厌氧条件下的生物脱毒、转化和矿化作用的研究成果。这些研究表明 ,由于硝基和偶氮基具有强烈的吸电子性 ,好氧条件下很难降解。但是 ,硝基和偶氮基芳香化合物在产甲烷菌群作用下较易还原脱毒 ,转化为相应的芳香胺类 ,其毒性要小几个数量级 ,因而有些毒性很高的芳香化合物废水可利用厌氧反应器处理 ,而且反应过程中发现一些芳香胺类化合物可被完全矿化 ,表明一些含氮芳香化合物可作为厌氧菌的碳源和能源 ,在厌氧条件下被完全生物降解。     

Transformation of phenol, catechol, guaiacol and syringol exposed to sodium hypochlorite

Germs, xenobiotics and organic matter that influence the colour, turbidity and organoloeptic properties of water are removed by chlorination. Unfortunately, chlorine oxidants including sodium hypochlorite, used in water treatment induce processes that partly convert the treated compounds to unwanted chlorinated derivatives. The purpose of this work was to analyse the efficiency of transformation of phenol, catechol, guaiacol and syringol exposed to sodium hypochlorite and determine the intermediates formed during oxidative conversion of these compounds. The analysis was performed in aerobic conditions, both in acidic (pH 4.0) and alkaline (pH 8.0) medium. The effectiveness of transformation was slightly higher in acidic in comparison to alkaline conditions. Some chlorophenols, such as 2-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol and pentachlorophenol were determined as the products of phenol conversion. Chlorophenols were also formed during catechol, guaiacol and syringol transformation by replacement of hydroxy and methoxy residues by chlorine atoms. Moreover, some chlorocatechols and chlorinated methoxyphenols were determined during catechol and methoxyphenols transformations. Higher concentrations of chlorinated compounds were observed in the alkaline environment during phenol transformation. Conversion of catechol and methoxyphenols generated higher amounts of chlorinated intermediates in the acidic medium. In samples carboxylic acids like acetic and formic acids were determined. The formation of these compounds was the result of the cleavage of aromatic structure of phenols.     

Synthesis of [13C]- and [14C]-labeled phenolic humus and lignin monomers

Natural phenolic monomers are ubiquitous in the environment and are involved in the stabilization of atmospheric carbon and the transformation of xenobiotics. Investigations on the stabilization of phenolic carbons and their environmental fate are hampered by the unavailability of commercial [13C]- and [14C]-labeled phenols. Here we report the complete chemical synthesis of the lignin and humus structural monomers p-coumaric, ferulic, and caffeic acids, p-hydroxybenzaldehyde, protocatechualdehyde, vanillin, catechol, and guaiacol, uniformly [13C]- or [14C]-labeled in the aromatic ring, starting from commercially available [U-ring-13C]- or [U-ring-14C]-labeled phenol. The synthesis of these compounds involved selective ortho-hydroxylation of the aromatic ring, Friedel-Crafts alkylation, and Knoevenagel condensation. [U-ring-13C]- or [U-ring-14C]-p-coumaric acid was synthesized via p-hydroxybenzaldehyde with a 75% yield with respect to phenol. Synthesis of [U-ring-13C]- or [U-ring-14C]-ferulic acid, consisting of six single steps via guaiacol and vanillin, had an overall yield of up to 45%. Uniformly ring-labeled caffeic acid was synthesized either via catechol and protocatechualdehyde in five single steps, yielding [U-ring-14C]-caffeic acid with a 37% yield, or via guaiacol, vanillin, and ferulic acid in seven steps, yielding [U-ring-13C]-caffeic acid with an 18% yield. Ferulic acid, [14C]-labeled at beta-C of the propenoic side chain, was synthesized from [2-14C]-malonic acid under Knoevenagel conditions with a 67% yield with respect to malonic acid. Demethylation of the [beta-14C]-ferulic acid with BBr3 in CH3CN resulted in [beta-14C]-caffeic acid with a 62% yield. All [U-ring-13C]-labeled phenolic products were analyzed by 13C nuclear magnetic resonance (13C-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).     

Historical record of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in marine sediment cores from Admiralty Bay, King George Island, Antarctica

This paper describes the first results of polycyclic aromatic hydrocarbons (PAHs) and spheroidal carbonaceous particles (SCPs) in sediment cores of Admiralty Bay, Antarctica. These markers were used to assess the local input of anthropogenic materials (particulate and organic compounds) as a result of the influence of human occupation in a sub-Antarctic region and a possible long-range atmospheric transport of combustion products from sources in South America. The highest SCPs and PAHs concentrations were observed during the last 30 years, when three research stations were built in the area and industrial activities in South America increased. The concentrations of SCPs and PAHs were much lower than those of other regions in the northern hemisphere and other reported data for the southern hemisphere. The PAH isomer ratios showed that the major sources of PAHs are fossil fuels/petroleum, biomass combustion and sewage contribution generally close to the Brazilian scientific station.     

Heterogeneous light-induced ozone processing on the organic coatings in the atmosphere

Many of the more recent studies concerning heterogeneous reactions of atmospheric interest, carry, in some cases, much more details but still follow the basic philosophy of the first pioneering studies. Therefore, in this study the accent is put on the additional complexities that arise when the aerosols of interest have more complex compositions. Hence, it is attempted to identify the products following the simultaneous ozone processing and light irradiation on particles coated with 4-phenoxyphenol in the presence of 4-carboxybenzophenone as a photosensitizer. In order to reveal a more complete picture on the fate of these aromatic compounds under controlled experimental conditions, different analytical tools such as gas chromatography coupled to mass spectrometry (GC–MS) and proton transfer reaction-mass spectrometry (PTR-MS) have been applied.Several surface bound products were identified via GC–MS and some of them (phenol, hydroquinone, catechol, 4-hydroxybenzoic acid, benzoic acid, fumaric acid, terephthalic acid, maleic acid, 1,2,4-trihydroxybenzene and 4,4′-oxydiphenol) confirmed with standards. The main volatile secondary products as identified by PTR-MS in this study were formic acid, phenol and p-benzoquinone.A reaction mechanism was proposed and density functional theory calculations were performed in order to elucidate the initial steps of the ozonolysis reaction on 4-phenoxyphenol in the presence of 4-carboxybenzophenone.     

Acute and chronic impacts caused by aromatic hydrocarbons on bacterial communities at Boa Viagem and Forte do Rio Branco Beaches, Guanabara Bay, Brazil

The bacterial community presented significantly different hydrocarbonoclastic activity under acute and chronic impacts. Benzoic acid, toluene, benzene and xylene were used in final concentrations of 5, 10 and 15 mM and bacterial biomass was quantified through protein dosage. Under acute impact, the highest biomass percentages occurred between the 11th and 14th days; under chronic impact, between the 20th and 29th days. Under acute and chronic impacts, the bacterial biomass presented higher nutritional specialization at Boa Viagem Beach, using the aromatic hydrocarbons up to a concentration of 15 mM. Under acute impact, the concentration of the hydrocarbons constituted a critical factor for the bacterial flora from Forte do Rio Beach, because biomass increases only occurred in concentrations of 5 mM; under chronic impact, the aromatic hydrocarbons induced the specialization and increased bacterial biomass for 15 mM toluene. Benzoic acid (15 mM) was used by the bacteria from Boa Viagem and Forte do Rio Branco Beaches.     

Occurrence of organic contaminants in sewage sludges from eleven wastewater treatment plants, China

This study presents the occurrence of 43 semi-volatile organic compounds (SVOCs) listed as priority pollutants by both China and the United States Environmental Protection Agency, in sewage sludges collected from eleven wastewater treatment plants (WWTPs) of mainland and Hong Kong, China. Thirty-six SVOCs were detected by gas chromatography coupled with mass spectrometer (GC-MS) and at least 14 in each sample. The most abundant compounds were phthalic acid esters (PAEs) and polycyclic aromatic hydrocarbons (PAHs) with total concentrations ranging from 10 to 114mgkg(-1) dry weight (d.w.) (with a mean of 30mgkg(-1) d.w.) and from 1.4 to 33mgkg(-1)d.w. (with a mean of 16mgkg(-1) d.w.), respectively, followed by chlorobenzenes, nitroaromatics, haloethers and halogenated hydrocarbons which occurred generally at concentrations lower than 10mgkg(-1) d.w. Large variations were observed between the concentrations of individual compounds as well as their total concentrations in sludge samples from different WWTPs. The highest values of sum concentration of 16 PAHs and of 6 PAEs were found in sewage sludge from Beijing. The mean total concentration of each class of SVOCs in sewage sludge from mainland was remarkably higher than that from Hong Kong. The concentrations of di(2-ethylhexyl) phthalate in 91% sludge samples met the limit (100mgkg(-1)d.w.) proposed by the Europe Union for land application, whereas the PAH concentrations of 64% sludge samples exceeded the maximum permissible concentration (6.0mgkg(-1)d.w.). The occurrence of SVOCs in this study are compared with other studies and their sources are discussed.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

压裂废水粘度对二氧化锰臭氧催化氧化处理特性的影响

通过FT-IR和GC-MS检测分析,表明了压裂废水中有机物主要以苯环结构为主的芳香类化合物和其他杂环化合物,苯环及杂环上的主要官能团包括酮、酯、羧酸、醛、酚、氨基等。同时,压裂废水中的粘度为常规水粘度的2~3倍。针对压裂废水高粘度和高COD污染水质特征,实验研究了压裂废水二氧化锰臭氧催化氧化处理特性以及粘度对处理效果的影响,研究结果表明,在粘度较高(2.2×10^-3Pa·s)压裂废水中,投加的化学药剂很难扩散,羟基自由基·OH的利用效率较低,处理效果较差。通过投加过硫酸钾(5 g/L)降粘后,可在很大程度上提高二氧化锰臭氧催化氧化的处理效果。通过对压裂废水中有机物分子量分布、FT-IR分析以及GC-MS分析可知,二氧化锰臭氧催化氧化处理压裂废水是通过激发羟基自由基,破坏水中有机物极性和有机物化学构造,将复杂长链有机物转变为简单有机物,其出水COD可达到国家污水综合排放标准中的二级排放标准。     

Spatial and Geographical Variations of Urban, Suburban and Rural Atmospheric Concentrations of Phenols and Nitrophenols (7 pp)

Goal, Scope and Background Atmospheric sampling (gas and particles) of 5 phenols (phenol, m-cresol, p-cresol, o-cresol, pentachlorophenol) and 15 nitrophenols (3-methyl-2-nitrophenol, 3-nitrophenol, 4-methyl-2-nitrophenol, 5-methyl-2-nitrophenol, 2-methyl-3nitrophenol, 3-methyl-4-nitrophenol, 2,6-dinitrophenol, bromoxynil, 2,5-dinitrophenol, 2,6-dinitro-p-cresol, 2,4-dinitrophenol, ioxynil, DNOC, 3,4-dinitrophenol, dinoseb) on XAD-2 resin (20 gr) and glass fibre filters, respectively, were performed in 2002 by using 'Digitel DA80' high volume samplers. These measurements were undertaken in order to show spatial and geographical variations of concentrations and the role of traffic in the emissions of these compounds to the atmosphere. Methods Sampling were performed in Strasbourg (eastern France), in its vicinity (Schiltigheim) and in Erstein. Sites were chosen to be representative of urban (Strasbourg), suburban (Schiltigheim) and rural (Erstein) conditions. Field campaigns were undertaken simultaneously in urban and suburban sites during all the seasons during 4 hours at a flow rate of 60 m3.h-1, which gives a total of 240 m3 of air per sample. Period of sampling varied between 06h00 to 10h00, 11h00 to 15h00 and 18h00 to 22h00 in order to evaluate a variation of concentration during automobile traffic between urban, suburban and rural areas. Gas and particle samples were separately Soxhlet extracted for 12 h with a mixture of CH2Cl2 / n-hexane (50:50 v/v), concentrated to about 1 mL with a rotary evaporated and finally dried under nitrogen. Dry extracts were dissolved in 1 mL of CH3CN. Before analysis, extracts were sylilated by using MTBSTFA. Analysis was performed by GC/MSD in the SIM mode. Results and Discussion Partitioning of phenolic compounds between gas and particle phases seems to be mainly correlated with vapour pressure. Among phenolic compounds analysed, phenol, p-cresol, pentachlorophenol and 2.4-dinitrophenol were detected in all samples and emissions from traffic seems to be the major source for the presence of these compounds to the atmosphere. No increase of concentrations in autumn tend to confirm this hypothesis since, with the use of domestic heating in colder months, increases of PAHs concentrations were observed and these compounds are known to be emitted by all combustion processes. Pentachlorophenol is a special case since this molecule is only used as wood preservative. Its presence in all atmospheric samples, whatever the locations and the period of time is the consequence of its persistence. Conclusions and Perspectives These measurements demonstrate that phenols and nitrophenols are emitted to the atmosphere and further measurements, in order to confirm their sources, their behaviour and their potential impact to the air quality and to human health should be undertaken especially since the literature collected is relatively old. Concentrations of pentachlorophenol measured are very low and, due to its toxicity, further investigations should be undertaken. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

Volatile organic compounds at swine facilities: A critical review

Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions.Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples.The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts.Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks.Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5 mg d⁻¹ kg⁻¹ pig at swine finishing barns and from 2.3 to 45.2 g d⁻¹ m⁻² at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates.Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.     

玉裂废水粘度对二氧化锰臭氧催化氧化处理特性的影响

通过FT-IR和GC—MS检测分析，表明了压裂废水中有机物主要以苯环结构为主的芳香类化合物和其他杂环化合物，苯环及杂环上的主要官能团包括酮、酯、羧酸、醛、酚、氨基等。同时，压裂废水中的粘度为常规水粘度的2～3倍。针对压裂废水高粘度和高COD污染水质特征，实验研究了压裂废水二氧化锰臭氧催化氧化处理特性以及粘度对处理效果的影响，研究结果表明，在粘度较高（2．2×10-3 Pa·s）压裂废水中，投加的化学药剂很难扩散，羟基自由基·OH的利用效率较低，处理效果较差。通过投加过硫酸钾（5g／L）降粘后，可在很大程度上提高二氧化锰臭氧催化氧化的处理效果。通过对压裂废水中有机物分子量分布、FT-IR分析以及GC—MS分析可知，二氧化锰臭氧催化氧化处理压裂废水是通过激发羟基自由基，破坏水中有机物极性和有机物化学构造，将复杂长链有机物转变为简单有机物，其出水COD可达到国家污水综合排放标准中的二级排放标准。     

Adsorption of phenolic compounds from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent

A water-compatible hypercrosslinked polymeric adsorbent (NJ-8) for adsorbing and removing phenolic compounds from their aqueous solutions was prepared. This product can be used directly without a wetting process. Its adsorption property toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was tested using the commercial Amberlite XAD-4 as a reference. The capacities of equilibrium adsorption for all four phenolic compounds on the NJ-8 from their aqueous solutions are around two times as high as that of Amberlite XAD4 within the temperature range 283-323 K, which may contribute to their micropore structure and the partial polarity on the network. Freundlich isotherm equations, as well as relative adsorption capacities and isosteric adsorption enthalpies for the four phenolic compounds, indicate that the adsorption of phenolic compounds on the NJ-8 resin is a physical adsorption process. Mini-column adsorption studies for phenol on Amberlite XAD4 and NJ-8 resins show that the breakthrough adsorption capacities are 0.54 and 0.99 mmol/ml, and the total capacities are 0.62 and 1.37 mmol/ml, while no extra acetone was needed to remove the adsorbed phenol from NJ-8 as from Amberlite XAD4.     

Occurrences and potential risks of 16 fragrances in five German sewage treatment plants and their receiving waters

Fragrances are used in a wide array of everyday products and enter the aquatic environment via wastewater. While several musk compounds have been studied in detail, little is known about the occurrence and fate of other fragrances. We selected 16 fragrance compounds and scrutinized their presence in Bavarian sewage treatment plants (STP) influents and effluents and discussed their ecological risks for the receiving surface waters. Moreover, we followed their concentrations along the path in one STP by corresponding time-related water sampling and derived the respective elimination rates in the purification process. Six fragrance substances (OTNE, HHCB, lilial, acetyl cedrene, menthol, and, in some grab samples, also methyl-dihydrojasmonate) could be detected in the effluents of the investigated sewage treatment plants. The other fragrances under scrutiny were only found in the inflow and were eliminated in the purification process. Only OTNE and HHCB were found in the receiving surface waters of the STP in congruent concentrations, which exceeded the preliminary derived environmental thresholds by a factor of 1.15 and 1.12, respectively, indicating potential risks. OTNE was also detected in similar concentration ranges as HHCB in muscles and livers of fish from surface waters and from ponds that are supplied with purified wastewater. The findings show that some fragrance compounds undergo high elimination rates, whereas others—not only musks—are present in receiving surface water and biota and may present a risk to local aquatic biota. Hence, our results suggest that the fate and potential effects of fragrance compounds in the aquatic environment deserve more attention.     

An evaluation of two fluorescence screening methods for the determination of chrysene metabolites in fish bile

Two screening methods, synchronous fluorescence spectrometry (SFS) and high performance liquid chromatography with fluorescence detection (HPLC-F), have been evaluated for their suitability in determining chrysene metabolites in fish bile. The optimal wavelength pair, excitation/emission 272/374 nm, for SFS measurements of chrysene metabolites was identified by analysis of bile taken from fish exposed to the pure compound. This analysis revealed in addition some information about the metabolite pattern. However, when bile from fish exposed to complex and environmentally relevant mixtures of polycyclic aromatic hydrocarbons (PAHs) was analysed using these methods, identification of the chrysene metabolites was poor. Analysis of bile taken from fish exposed to single PAHs identified other three- and four-ring aromatics as the main interfering compounds. Both methods were equally able to discriminate between impacted and reference sites by determination of relative concentrations of fluorescent three- and four-ring aromatics.     

Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments

Aqueous-phase photooxidation of glyoxal, a ubiquitous water-soluble gas-phase oxidation product of many compounds, is a potentially important global and regional source of oxalic acid and secondary organic aerosol (SOA). Reaction kinetics and product analysis are needed to validate and refine current aqueous-phase mechanisms to facilitate prediction of in-cloud oxalic acid and SOA formation from glyoxal. In this work, aqueous-phase photochemical reactions of glyoxal and hydrogen peroxide were conducted at pH values typical of clouds and fogs (i.e., pH=4–5). Experimental time series concentrations were compared to values obtained using a published kinetic model and reaction rate constants from the literature. Experimental results demonstrate the formation of oxalic acid, as predicted by the published aqueous phase mechanism. However, the published mechanism did not reproduce the glyoxylic and oxalic acid concentration dynamics. Formic acid and larger multifunctional compounds, which were not previously predicted, were also formed. An expanded aqueous-phase oxidation mechanism for glyoxal is proposed that reasonably explains the concentration dynamics of formic and oxalic acids and includes larger multifunctional compounds. The coefficient of determination for oxalic acid prediction was improved from 0.001 to >0.8 using the expanded mechanism. The model predicts that less than 1% of oxalic acid is formed through the glyoxylic acid pathway. This work supports the hypothesis that SOA forms through cloud processing of glyoxal and other water-soluble products of alkenes and aromatics of anthropogenic, biogenic and marine origin and provides reaction kinetics needed for oxalic acid prediction.