Analysis of phenols and nitrophenols in rainwater collected simultaneously on an urban and rural site in east of France

The behaviour of phenols and nitrophenols in the atmosphere is of concern for environmental research as these are known to be toxic to humans and wildlife. To increase the knowledge about these compounds, the concentrations of 20 phenols and nitrophenols in rainwater were studied in an urban (Strasbourg) and a rural (Erstein) site in Eastern France.The wet rain samples were collected on a weekly basis between January 2002 and July 2003, and analyzed for phenols and nitrophenols using SPME and gas chromatography coupled to mass spectrometry. The compounds were derivatized with MDBSTFA directly in the injection port of the gas chromatograph.Total concentrations ranged from 0 to 1383 µg L^− 1 in Strasbourg and from 0 to 1215 µg L^− 1 in Erstein. These concentrations are in the same range than those measured in other studies, but considerably higher than the concentrations measured for pesticides (about 10 times) and polycyclic aromatic hydrocarbons (about 1000 times) on the same sites and at the same period.Phenols, except for o-cresol, were generally less concentrated than nitrophenols. o-Cresol was one of the major compounds, probably due to its role as raw material in pesticide production. The concentrations of phenols and nitrophenols were found to vary with time. No seasonal trend was observed, but significant correlations with rainfall amount were identified.     

Gas chromatographic-mass spectrometric identification of phenols and aromatic acids in river waters

The ethyl acetate extracts of water samples from two urban rivers in Tokyo were analyzed for phenols and aromatic acids by using a combined gas chromatograph-mass spectrometer after separating by solvent extraction and silica gel column chromatography. The following phenols and aromatic acids were identified: pentachlorophenol, bisphenol A, phthalic acid, trimesic acid, p-hydroxybenzoic acid, vanillic acid, syringic acid, p-coumaric acid, and ferulic acid. The presence of o- and m-hydroxybenzoic acids were suggested by mass fragmentography. The sources of those compounds are considered.     

Phenolic compounds of Pinus laricio needles: A bioindicator of the effects of prescribed burning in function of season

Fire is a dominant ecological factor in Mediterranean-type ecosystems. Forest management includes many preventive tools, in particular for fire prevention, such as mechanical treatments and prescribed burning. Prescribed burning is a commonly used method for treating fuel loads, but fuel reduction targets for reducing wildfire hazards must be balanced against fuel retention targets in order to maintain habitat and other forest functions. This approach was used on Pinus nigra ssp laricio var. Corsicana, a pine endemic to Corsica of great ecological and economic importance. Many studies of plant phenolic compounds have been carried out concerning responses to various stresses. The aim of this study was to understand i) the effects of prescribed burning 1 to 16 months later and ii) the effects of the seasonality of burning, spring or fall, on the production of phenolic compounds in Pinus laricio. After prescribed burning conducted in spring, Pinus laricio increases the synthesis of total phenolic compounds for a period of 7 months. The increase is greater after spring-burning than fall-burning. With regard to simple phenols, only dihydroferulic acid responds about 1 year after both types of prescribed burning. The causes of these increases are discussed in this paper. Total phenolic compounds could be used as a bioindicator for the short-term response of Pinus laricio needles to prescribed burning. Simple phenols may be useful for revealing the medium-term effects of prescribed burning. The results of this study include recommending forest managers to use prescribed burning in the fall rather than spring to reduce fuel loads and have less impact on the trees.     

Dissolved organic compounds in reused process water for steam-assisted gravity drainage oil sands extraction

The in situ oil sands production method called steam-assisted gravity drainage (SAGD) reuses process wastewater following treatment. However, the treatment and reuse processes concentrate contaminants in the process water. To determine the concentration and dynamics of inorganic and organic contaminants, makeup water and process water from six process steps were sampled at a facility employing the SAGD process in Alberta, Canada. In the groundwater used for the makeup water, the total dissolved organic carbon (DOC) content was 4 mg/L. This significantly increased to 508 mg/L in the produced water, followed by a gradual increase with successive steps in subsequent water treatments. The concentrations and dynamics of DOC constituents in the process water determined by gas chromatography-mass spectrometry showed that in the produced water, volatile organic compounds (VOCs) such as acetone (33.1 mg/L) and 2-butanone (13.4 mg/L) predominated, and there were significant amounts of phenolic compounds (total 9.8 mg/L) and organic acids including naphthenic acids (NAs) corresponding to the formula C_nH_2n+ZO_X for combinations of n = 4 to 18, Z = 0 and −2, and X = 2 to 4 (53 mg/L) with trace amounts of polycyclic aromatic hydrocarbons (PAHs) such as naphthalene and phenanthrene. No organic contaminants, except for saturated fatty acids, were detected in the groundwater. The concentration of DOC in the recycled water was 4.4-fold higher than that in the produced water. Likewise, the total concentrations of phenols and organic acids in the recycled water were 1.7- and 4.5-fold higher than in the produced water, whereas the total concentrations of VOCs and PAHs in the recycled water were reduced by over 80%, suggesting that phenols and organic acids are selectively concentrated in the process water treatment. This comprehensive chemical analysis thus identified organic constituents that were concentrated in the process water and which interfere with subsequent water treatments in the SAGD process.     

Oxidative transformation of aqueous phenolic mixtures by birnessite-mediated catalysis

The catalytic efficiency of birnessite in the removal of catechol, hydroxytyrosol, methylcatechol and m-tyrosol, four phenols commonly present in polluted wastewaters, was studied in mono-substrate solutions or in mixtures of two, three, and four substrates. In single phenolic solutions the transformation order of phenols was catechol>hydroxytyrosol>methylcatechol>m-tyrosol. With phenolic mixtures different responses were observed and the amount of each phenol transformed and the crossing effects among the various phenols depended on the type and number of phenols present in the mixture. In particular, general inhibitory effects were observed for hydroxytyrosol and m-tyrosol that were transformed less when present in combination with the other phenols. By contrast the effects by the presence of more than one phenol were basically annulled for catechol and methylcatechol at 24 h incubation in all the mixtures. A simultaneous, but often no stoichiometric, release of soluble Mn2+ in the reaction mixtures occurred. The multi-substrate systems were designed to mimic birnessite-mediated oxidative processes that could occur under field conditions. Therefore they could be of great interest to environmental and soil science. The use of birnessite as a potential tool for an effective detoxification and recovery of phenol-polluted systems could be also envisaged.     

Persistent chemicals in pulp mill effluents: Occurrence and behaviour in an activated sludge treatment plant

In wastewater effluents of a Swiss pulp mill more than 50 organic chemicals were identified including chlorinated phenols, chloroform, chlorinated terpenoids and chlorinated resin acids. Quantitative determinations were carried out to investigate the behaviour of the most abundant constituents during wastewater treatment in an activated sludge process. In particular, the chlorinated compounds were only partly eliminated. The lipophilic chlorinated phenols were physically absorbed to some extent into the activated sludge biomass. The importance of this nonbiological elimination mechanism was evaluated by applying distribution coefficients between activated sludge particles and water which were determined for a series of chlorinated phenols. Chloroform and other purgeable compounds were removed mainly by transfer into the ambient air. The impact of the persistent wastewater constituents on the water quality in the receiving River Aare was assessed. It was estimated that the concentrations of chlorinated phenols in the river caused by the discharge of the treated pulp mill wastewater are about 10 times lower than the levels of pentachlorophenol which typically occur in Swiss rivers receiving effluents from municipal wastewater treatment plants.     

Biological lagooning of phenols-containing oil shale ash heaps leachate

In the course of the present study the biological treatment of leachate from oil shale semicoke ash heaps in a wastewater lagoon was investigated. The lagooning process was simulated by laboratory-scale batch processes and a lagoon, by applying different aeration conditions at 20°C.

Treatment in the lagoon significantly reduced chemical oxygen demand (COD), biochemical oxygen demand (BOD) and phenols in the leachate. A removal of 55–64% of COD was achieved. The removal of phenols, estimated on the basis of identified phenolic compounds, was 80–88%. The best removal of COD, up to 70%, was achieved in the intermittently aerated batch, while in the non-aerated batch the removal was 41%. In the intermittently aerated batch the removals of phenol, methylphenols and dimethylphenols were on the average from 95 to over 99%. All the tested systems showed lower removals of resorcinols compared to those of monohydric phenols.

This study indicates that leachate from oil shale semicoke ash heaps could be treated in an aerated lagooning system, and that the biological treatment of the high pH leachate is feasible without pH adjustment.     

The determination of phenols in aqueous effluents

A method is described for the determination of monohydric and dihydric phenols in aqueous effluents. The phenols were extracted into methyl isobutyl ketone, the trimethylsilyl ethers prepared, separated by gas—liquid chromatography and detected by a flame ionization detector. Complete separation of phenol, cresols, xylenols, ethylphenols and dihydric phenols was achieved using dual stainless steel columns packed with Chromosorb W (AW-DCMS) coated with 5 per cent tri-2,4-xylenyl phosphate and by linear temperature programming from 75° to 125°C at 1.5°C min⁻¹; concentrations down to 0.1 mg l⁻¹ of each phenol in the original sample could be determined. The results obtained by the gas chromatographic method were compared with those using standard colorimetric methods of analysis for carbonization effluents arising from different sources. The method is generally applicable to wastes containing phenols.     

Oxidation of aromatic compounds by haemoglobin

Klibanov et al. have recently developed new methods for the elimination of phenols and aromatic amines. These involve two enzyme systems. Polyphenol oxidase with oxygen and horseradish peroxidase (HRP) with hydrogen peroxide, which permit the precipitation of these pollutants from wastewaters. Another study, using HRP, has shown that phenols at the low concentration usually found in drinking water, can be removed but with no apparent precipitate. However, these processes seem to be limited by the cost of the catalyst. In this work, the possibilities for oxidation of a phenolic compound such as methoxyphenol, by free or immobilized HRP, haemoglobin or blood haemolysate, in the presence of hydrogen peroxide, were investigated. Results indicate that haemoglobin can replace HRP with regard to its activity and cost. Removal of phenol was studied with free blood-haemolysate. More than 90% of this aromatic compound disappeared. Two conversion products were identified, 4,4′- and 2,2′-dihydroxybiphenyl, but not in sufficient quantity to account for all phenol removed.Nearly complete removal of benzidine and o-dianisidine, two carcinogenic aromatic amines often found in surface water, was obtained with immobilized blood haemolysate.Enzymatic oxidation by haemoglobin appear to be efficient and useful in the removal of micropollutants from drinking water.     

HDX-8树脂吸附水中痕量酚的研究

研究了HDX 8树脂对苯酚的吸附性能 ,最大静态吸附容量为 2 2 3.5mg/g .柱长 1 0cm ,内径 1 .0cm ,内装HDX 8树脂的吸附柱 ,在酸性条件下 ,能有效地吸附水中的痕量酚 ,负载柱可用 0 .1mol/LNaOH溶夜定量解吸 ,富集倍率达 1 0 0 .研究认为 ,HDX 8吸附树脂既可有效去除水中酚污染 ,又可用于痕量分析中酚的定量富集     

Phenolindex – ein sinnvoller Parameter für die Altlastenbewertung?

Alkyl phenols are toxic, water soluble organic compounds with a possible low biodegradation potential under reducing conditions. They are by-products of coking processes and main components of tars and creosote. However, they have been widely neglected to be a problem. The alkyl phenols do not belong to the EPA-phenols, except for 2,4-Dimethyl phenol. This means, that no standard analytical procedures are currently available. The often applied sum parameter “Phenolindex” does not fully account for those compounds. For a typical contamination case only a fraction of the total phenols are recovered by this parameter. On the other hand the index is positive for other coexisting organic compounds. The threshold level of phenolindex is 50 μg/l, which means that the actual concentration of phenols can range from the detection limit up to 250 μg/l. As a consequence, the use of the parameter as the only indicator for a plume will lead to a wrong estimation of the contamination problem.     

Sorption of phenols to dissolved organic matter investigated by solid phase microextraction

The sorption of phenol and different halogenated phenols to natural organic matter of a brown water lake (HO14), of a compost extract, of Aldrich humic acid (Aldrich-HA), and to the protein bovine serum albumin (BSA) was investigated using solid phase microextraction (SPME). The limit of determination for the SPME analysis was < 15 microg/l for all phenols investigated. The extraction coefficients K(F) were calculated according to a first-order extraction kinetics. In general, the extraction equilibrium was established faster due to the presence of dissolved organic matter (DOM). The highest sorption capacity of phenols was observed for BSA with log K(OC) values in the range between 2 and 6. For the compost extract and HO14 only a small sorption of the investigated phenols was determined. On the other hand, Aldrich humic acid showed a reasonable sorption of phenols with log K(OC) values between 2 and 3. The sorption to DOM decreased when the pH of the solution was increased.     

Removal of phenols from a foundry wastewater using horseradish peroxidase

Horseradish peroxidase (HRP) catalyses the oxidation of phenols by hydrogen peroxide resulting in the formation of water-insoluble polymers which can be separated by coagulation and sedimentation. The feasibility of the enzyme process to treat a foundry wastewater containing 3.5 mM of total phenols (330 mg/l as phenol) was examined. Two enzyme stocks of different purities were used but total phenols removal was independent of enzyme purity. For both stocks, 97 to 99% of the phenolic contaminants were removed, despite the presence of other contaminants such as organic compounds and iron in the waste matrix. The quantity of HRP required for this degree of treatment was in the same range as for the treatment of a synthetic wastewater containing an equal amount of pure phenol. Polyethylene glycol, a chemical additive, reduced enzyme inactivation, allowing a 22-fold reduction in the amount of HRP required for 99% removal of phenols from the foundry waste. Residual chemical oxygen demands (COD) varied depending on the enzyme source. The high purity HRP achieved more than 65% removal of COD, but due to a high concentration of other organic matter present in the low purity HRP, no reduction in COD was achieved with this enzyme source. A comparison was made between enzyme treatment and oxidation using Fenton's reagent. Enzyme cost must be significantly reduced in order to make the enzyme treatment process economically competitive.     

Removal of phenolics in olive mill wastewaters using the white-rot fungus Pleurotus ostreatus

Olive mill wastewaters (OMW) present a major environmental problem. The large amounts generated, combined with the high phenols and chemical oxygen demand concentrations, are the main difficulties in finding a solution for the management of these wastewaters, which are dangerous for the environment. The phenols, which are contained in the OMW have a structure similar to lignin, which makes them difficult to biodegrade. Lignin can be degraded only by a few microorganisms, such as "white-rot" basidiomycete, which produce manganese (MnPs) and lignin peroxidases (LiPs) and laccases that are responsible for the oxidisation of lignin compounds. The capability of Pleurotus ostreatus to degrade phenols of OMW in different conditions such as in sterilized and thermally processed (at 100 degrees C) wastewater, with and without dilution, is investigated in this work. According to the experimental results P. ostreatus removed phenols from the culture medium, under all different conditions that were examined. The degradation of phenols reached up to 78.3% for the sterilized and 50% diluted OMW, 66.7% and 64.7% for the thermally processed OMW, with and without dilution, respectively. The effect of pre-treatment of OMW on the performance of anaerobic digestion is also assessed, as methanogenic bacteria are seriously affected by the presence of phenol compounds. The pre-treated wastewater was shown to be more amenable to a subsequent anaerobic digestion.     

Effects of soil type, irrigation volume and plant species on treatment of log yard run-off in lysimeters

Wet storage of timber and pulpwood produces large quantities of run-off water. A study was conducted to determine the purification efficiency of soil-plant systems for log yard run-off. Sixteen 1200-l lysimeters (1.2 m deep soil columns) with clay or sand soil were planted with willow (Salix sp.) or alder (Alnus glutinosa), and irrigated with run-off from a Norway spruce (Picea abies) log yard. Drainage water was analysed for total organic carbon (TOC), phenols, total P and total N in order to determine concentrations and levels of retention. High retention of TOC, phenols and P occurred in the lysimeters, but no clear differences between willows and alder or clay and sand were identified. Lysimeters with high levels of irrigation showed greater retention than those with low levels. Soil-plant systems using willow and alder could provide an alternative for log yard run-off purification: the key requirement is to optimise irrigation rather than manipulate the plants or soils.     

Oxidative transformation of phenols in aqueous mixtures

The transformation by an oxidoreductase (a laccase from Rhus vernificera) of a mixture of four phenols (catechol, methylcatechol, m-tyrosol and hydroxytyrosol) that simulates a typical wastewater derived from an olive oil factory was investigated. Results achieved in this study confirm that laccase-mediated transformation of phenols depends on the nature and the initial concentration of the involved phenol, the time course of the reaction, and mainly, on the complexity of the phenolic incubation mixture. Actually, the four phenols each have a completely different response to enzyme action both in terms of quantitative and kinetic transformation. For example, after 24-h incubation, methylcatechol was completely removed, whereas 30% of untransformed hydroxytyrosol and catechol and more than 65% of m-tyrosol were still present in the reaction mixture. A reduction of enzyme activity occurred for all phenols after enzymatic oxidation. No correspondence between phenol transformation and disappearance of enzymatic activity was observed, thus suggesting that different mechanisms are probably involved in the laccase-mediated transformation of the four phenols. The behavior of phenols became more complex when an increasing number of phenols was present in the reaction mixture, and even more so when different concentrations of phenols were used. Competitive effects may arise when more than one phenol is present in the reaction solution and interacts with the enzyme.     

Is phenol condensation one of the major pathways in the formation of polychlorinated dibenzofurans in municipal waste incinerators?: Model prediction vs. field observation

The role of phenol condensation pathways in the formation of polychlorinated dibenzofurans (PCDF) in a municipal waste incinerator was assessed by comparing predicted PCDF homologue and isomer patterns with those obtained from the incinerator. A two-phenol condensation model, dependent only on the distribution of phenols, was used to predict the distributions of PCDF congeners in the incinerator. Complete distributions of phenols and PCDF congeners were obtained from the incinerator. To quantify the degree of agreement between obtained isomer distributions and those predicted by the model, R-squared values from linear correlations were calculated for the dichlorinated- through hexachlorinated-isomers. They ranged from 0.001 to 0.1. Agreement between obtained and predicted PCDF isomers was very poor for all homologues, suggesting that phenol condensation pathways are unlikely to be the primary route in the formation of PCDF in the incinerator. However, dibenzofuran (DF) is likely to be produced from a condensation of two phenols. This paper shows the use of PCDF homologue and isomer patterns calculated by the two-phenol condensation model for testing PCDF formation mechanism attribution in a municipal waste incinerator.     

Phenols in anaerobic digestion processes and inhibition of ammonia oxidising bacteria (AOB) in soil

This study focuses on the presence of phenols in digestate from seven Swedish large-scale anaerobic digestion processes and their impact on the activity of ammonia oxidising bacteria (AOB) in soil. In addition, the importance of feedstock composition and phenol degradation capacity for the occurrence of phenols in the digestate was investigated in the same processes. The results revealed that the content of phenols in the digestate was related to the inhibition of the activity of AOB in soil (EC(50)=26 microg phenols g(-1) d.w. soil). In addition, five pure phenols (phenol, o-, p-, m-cresol and 4-ethylphenol) inhibited the AOB to a similar extent (EC(50)=43-110 microg g(-1) d.w. soil). The phenol content in the digestate was mainly dependent on the composition of the feedstock, but also to some extent by the degradation capacity in the anaerobic digestion process. Swine manure in the feedstock resulted in digestate containing higher amounts of phenols than digestate from reactors with less or no swine manure in the feedstock. The degradation capacity of phenol and p-cresol was studied in diluted small-scale batch cultures and revealed that anaerobic digestion at mesophilic temperatures generally exhibited a higher degradation capacity compared to digestion at thermophilic temperature. Although phenol, p-cresol and 4-ethylphenol were quickly degraded in soil, the phenols added with the digestate constitute an environmental risk according to the guideline values for contaminated soils set by the Swedish Environmental Protection Agency. In conclusion, the management of anaerobic digestion processes is of decisive importance for the production of digestate with low amounts of phenols, and thereby little risks for negative effects of the phenols on the soil ecosystem.     

水中氯代酚类化合物的生物降解研究

从扬子石化公司污水处理厂的曝气池出口处取活性污泥样品,经驯化、培养、分离得到能降解氯代酚类化合物的复合菌.利用驯化的复合菌群进行受氯代酚污染水体的生物修复试验,结果表明,该复合茵群较自然水体中的混合细菌对氯代酚有更强的耐受性.在低浓度下2-氯酚最易被降解,去除率达到了97%;在高浓度下3-氯酚最易被降解,去除率达到了82%.浓度对3种氯代酚的降解效率影响较大.在苯酚与3-氯酚共存的条件下,苯酚优先被微生物利用,随后3-氯酚才被分解,但对3-氯酚的降解率有所提高.当2-氯酚与3-氯酚等量共存时,复合菌的代谢效率有所降低,二者的联合作用表现为叠加作用.     

Measurement of phenols dearomatization via electrolysis: The UV-Vis solid phase extraction method

Dearomatization levels during electrochemical oxidation of p-methoxyphenol (PMP) and p-nitrophenol (PNP) have been determined through UV-Vis spectroscopy using solid phase extraction (UV-Vis/SPE). The results show that the method is satisfactory to determine the ratio between aromatic compounds and aliphatic acids and reaction kinetics parameters during treatment of wastewater, in agreement with results obtained from numerical deconvolution of UV-Vis spectra. Analysis of solutions obtained from electrolysis of substituted phenols on antimony-doped tin oxide (SnO₂Sb) showed that an electron acceptor substituting group favored the aromatic ring opening reaction, preventing formation of intermediate quinone during oxidation.