Determination of halogenated phenols in raw and potable water by selected ion gas chromatography-mass spectrometry

Pentafluorobenzylation and in situ acetylation are compared in the determination of phenol and halogenated phenols in water samples. The latter technique is considered superior to the former for determining phenols at the ng/L level because of less background interference and better recoveries (80% or better except for pentachlorophenol and trichloroguaiacol which had recoveries of about 60%). Further evaluation of the in situ technique by electron capture gas chromatography and gas chromatography-mass spectrometry shows that the latter, in the selected ion monitoring mode, is more suitable because, unlike GC-ECD, it can confirm and quantitate all phenols. In particular, GC-ECD could not detect even high levels of phenol and the monohalogenated phenols. Phenols at 5-473 ng/L were detected in some Canadian drinking water supplies by the in situ acetylation technique combined with GC-MS.     

Human exposure to perfluorinated compounds in Catalonia, Spain: contribution of drinking water and fish and shellfish

In this study, the concentrations of 15 perfluorinated compounds (PFCs) were analyzed in 30 water samples collected in Catalonia (Spain) at three stages of the drinking water treatment process in several water purification plants. In addition, the concentrations of 13 PFCs were determined in samples of fish and shellfish collected from coastal areas of Catalonia. The intake of PFCs through both pathways, drinking water intake and fish and shellfish consumption, was also estimated. In water samples, the highest mean concentrations corresponded to perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) (1.81 and 2.40 ng/L, respectively), whereas perfluorodecanosulfonate (PFDS) and perfluorotetradecanoic acid (PFTDA) were under their respective limits of detection in all analyzed samples. The results show that although the current treatment processes caused slight reductions in PFC concentrations, these processes did not mean significant changes in the amounts of PFCs already contained in the raw water. Among the analyzed PFCs in fish and shellfish, only seven compounds could be detected in at least one composite sample. PFOS showed the highest mean concentration (2.70 ng/g fw), being detected in all species with the exception of mussels. With regard to PFOA (mean, 0.074 ng/g fw), the highest concentrations were detected in prawn and hake (0.098 and 0.091 ng/g fw, respectively). The current exposure to PFCs through consumption of fish and shellfish indicates that it should not be of concern for the consumers. The amounts ingested are well below the recommended tolerable daily intakes, at least for those PFCs for which information is available.     

Enhanced Phenol and Chlorinated Phenols Removal by Combining Ozonation and Biodegradation

Water treatment for wastewater containing phenols and their chlorinated variations has attracted important research efforts. Phenol??s high toxicity makes them a good model to test possible water treatment based on biological and/or chemical methods. High concentrations of phenols may be treated by pure biological schemes. However, chlorinated phenols are very toxic for many microorganisms. Therefore, mixed treatment trains can be proposed to solve the treatment of this class of organics. In this study, the ozonation was used as pretreatment to decompose chlorinated phenols. Besides, this study describes how the microbial consortiums were adapted to handle ozonation by-products. The biodegradation of different phenol concentrations from 50 to 1,500?mg/L was evaluated using preadapted microbial consortia in batch and in a trickling packed-bed reactor (TPBR). Under batch conditions, phenol was efficiently removed up to 500?mg/L. For every phenol concentration evaluated, higher degradation rates were obtained in TPBR. The chlorophenols were found to be poorly degraded by the pure biological treatment, 4-CPh was not degraded during the biological process and 2,4-DCPh was only 40?% degraded after 250?h of culture. By combining the chemical (as pretreatment) and the biological processes, 85?% of 4-CPh was removed, while the degradation of the 2,4-DCPh was enhanced from 40 to 87?%. The predominant bacteria found in the preadapted cultures were Xanthomonas sp., Ancylobacter sp., and Rhodopseudomonas. Total treatment period was reduced from several weeks to some days. This information reflects the benefits offered by the mixed water treatment train proposed in this paper.     

One-step sample preparation technique for broad spectrum gas chromatographic/mass spectrometric determination of organic priority pollutants in water

A rapid and cost-effective sample preparation technique is described for the qualitative and quantitative determination of a broad spectrum of organic contaminants in water. The technique involves simultaneous-in-situ acetylation of phenols with acetic anhydride and one-step extraction of phenol acetates and basic and neutral organic compounds from water. The extract is concentrated and analyzed by gas chromatography/mass spectrometry. The recovery and precision data of selected base, neutral, and phenolic compounds are given. The advantages and disadvantages of the in-situ acetylation/extraction technique are discussed.     

Yeasts used as fining treatment to correct browning in white wines

White wine was subjected to several fining treatments using baker's yeast at concentrations of 0.5, 1, 2, 3, 4, and 5 g/L. At all these concentration levels, the yeasts decreased the color of the wine in different degrees. The wine samples treated with the higher yeast concentration were subjected to analysis of phenolic compounds by HPLC and found to exhibit significantly decreased contents of vanillic, syringic and c-coutaric acids, and procyanidins B2 and B4, and colored compounds eluted at high retention times. The efficiency of the yeast-based fining treatment (1 g/L) was compared with traditional treatments such as those involving the use of activated charcoal or PVPP, which were employed at the usual concentrations in Sherry winemaking. This yeast treatment was found to provide results similar to those of the activated charcoal treatment in terms of A(420). Likewise, significant differences in the degree of retention of various phenols were observed among the three treatments compared. Finally, the wine samples obtained with the different treatments were subjected to a sensory panel. All the wines were found to exhibit improved color, aroma, and flavor with respect to the untreated samples, although the treatment using yeast at 1 g/L provided the best results in terms of aroma.     

微酸性电解水结合壳聚糖对水蜜桃护色保鲜的效果

为了防止水蜜桃(Prunus persicaL.Batsch)采后的果肉颜色变化而严重影响其商品价值。该研究以南汇水蜜桃为材料,分别利用自制羧甲基壳聚糖复合保鲜剂,以及微酸性电解水对水蜜桃进行护色保鲜处理,并对冷藏条件下(2℃)水蜜桃果肉颜色及与颜色品质变化相关的指标进行了检测,同时还利用核磁共振成像(MRI)合成T2-MAP图研究了冷藏开始和结束后水蜜桃内部变化的规律。结果表明,在贮藏结束后,对照组果肉颜色的L*值、H*值、C*值分别是羧甲基壳聚糖复合保鲜剂和微酸性电解水处理组的85%～91%、85%～93%和114%～122%(p<0.05)。显然,羧甲基壳聚糖复合保鲜剂和微酸性电解水由于可以抑制水果自身乙烯的产生,减少水果的细胞膜透性和T2-MAP图中T2弛豫常数的变化,降低了多酚氧化酶(PPO)活性的增加速度,减少了酚类物质的累积,进而延缓了果肉的变色。另外,与仅用电解水处理相比,结合羧甲基壳聚糖处理具有较好的护色保鲜效果。通过该研究,可以为提高采后南汇水蜜桃的果肉护色保鲜效果提供参考。     

桉树与格木混交初期土壤理化性质的变化

以2年生桉树人工林及桉树、格木混交林为对象,对其造林初期林地土壤理化性质的变化进行研究,探讨其土壤理化性质、土壤酶活性与土壤酚类物质间的关系。结果表明:(1)两种林分根区土壤pH值较小,0—20cm土壤pH值大于20—40cm,混交林林间0—20cm土壤自然含水率、容重、最大持水量、总孔隙度、通气度均较桉树纯林大;对林间20—40cm土层而言,桉树×格木混交林容重、总孔隙度、通气度、排水能力均比桉树纯林大,自然含水率、最大持水量相反。(2)混交林林间0—20cm土壤脲酶活性最大,为1.46mg/(g·h),脲酶、磷酸酶及多酚氧化酶活性均表现为桉树根区大于格木根区,且较桉树纯林桉树根区大。(3)桉树纯林根区总酚、复合酚含量最大,混交林林间0—20cm水溶酚含量最大,土壤水溶酚含量范围为0.62~2.04μg/g。桉树纯林造林初期土壤中酚类物质含量较低,未造成土壤酚类物质的积累;桉树与格木混交初期能改善土壤理化性质,提高土壤酶活性;土壤理化性质、土壤酶活性与酚酸物质含量间存在着一定的相关性。     

电解水对荞麦芽酚酸含量及抗氧化能力的影响

为了能够更好地将发芽荞麦用作制备功能食品的原料,本研究采用理化指标不同的电解水制备荞麦芽,考察荞麦的发芽率及芽长、总酚含量、DPPH和ABTS自由基清除能力,以及铁离子还原力在发芽期间的动态变化,并分析各处理组发芽第7天荞麦芽中游离酚和结合酚种类和含量。结果表明,在7 d观测期内,电解水有利于荞麦发芽及生长。不同评价方法测定荞麦芽抗氧化能力的结果显示,pH值11.13电解水处理组发芽1~3 d荞麦芽总酚含量及抗氧化水平均显著高于对照组(P<0.05),而pH值3.21、pH值5.02和pH值9.02电解水处理组发芽5~7 d荞麦芽总酚含量及抗氧化水平均显著高于对照组(P<0.05)。各处理组荞麦芽中主要的游离酚均为绿原酸,且电解水处理组荞麦芽游离绿原酸含量均显著高于对照组(P<0.05)。自来水处理组荞麦芽主要结合酚为香豆酸,而电解水处理组荞麦芽主要结合酚为咖啡酸。本研究结果为电解水应用于功能性荞麦芽的制备提供了理论依据。     

Investigation of the antioxidant behavior of air- and freeze-dried aromatic plant materials in relation to their phenolic content and vegetative cycle

The total phenolic and flavonoid content of the aerial parts of five aromatic plants harvested at different periods was estimated, and their antioxidant capacity was evaluated. Major phenolic compounds present in their extracts were determined by RP-HPLC. The results demonstrated different amounts of total phenolic compounds and various degrees of antioxidant activity depending on the plant species, the time of harvest, and the drying method employed. Extracts from air-dried Mentha viridis L., Origanum majorana L., and Rosmarinus officinalis L. demonstrated the greatest efficacy during the flowering stage, in which the identified flavonoids were found in significantly higher amounts, whereas phenolic acids were found in their lowest concentration. Extracts from air-dried Laurus nobilis L. and Foeniculum vulgare Mill were less efficient in terms of antioxidant activity, with the highest values being observed during the early fruiting stage. This stage was characterized by the lowest flavonoid content and high phenolic acid content, except for L. nobilis L. extracts. Overall, the amount of identified phenolic acids did not vary considerably within the investigated year. The total phenolic concentration in all plant extracts decreased significantly when freeze-dried rather than air-dried samples were used. The HPLC analysis further supported the above for most of the phenolic compounds present in the extracts, except for hydroxybenzoic acids, which were better retained during the freeze-drying process.     

Monitoring Methyl Tertiary Butyl Ether (MTBE) and other Organic Micropollutants in Groundwater: Results from the Danish National Monitoring Program

The paper presents results of analyses of 7671 groundwater samples collected from 1115 screens in the period 1993 to 2001 for the Danish National Groundwater Monitoring Program. In Denmark groundwater is widely used for drinking water and the objectives of the monitoring program is to describe the present conditions, the development of, and the impacts on the groundwater. The design of the Danish National Groundwater Monitoring Program is described and data are provided. Data originate from monitoring areas and are supplemented with data from the waterworks' control of nearly 6000 water supply wells. In addition to pesticides there is a series of other organic compounds that must be considered in relation to possible groundwater contamination. Sources of these compounds and their importance in relation to groundwater contamination is discussed on the basis of the monitoring data. The organic micropollutants monitored are grouped according to chemical properties: aromatic hydrocarbons, chlorophenols, detergents, halogenated aliphatic hydrocarbons, ethers (MTBE), phenols, and phthalates. The most frequently found compounds were toluene (18.7% ), phenol (14.6%), xylene (10.9), trichloromethane (9.5%), and benzene (in 8.8% of the screens monitored). The five compounds most frequently found at a concentration above the maximum residue limits (MRL) for drinkingwater were: dibuthylphthalate (28%), phenol (14%), 2,4-dichlorophenol (10%), trichloromethane (10%), pentachlorophenol (7% of findings exceeding the MRL for drinkingwater). Overall, one or several compound was observed at least once in 57.8% of the 1115 screens monitored within the period 1993–2001. On a yearly basis the median finding frequency was 19%.     

Smoke-derived taint in wine: the release of smoke-derived volatile phenols during fermentation of Merlot juice following grapevine exposure to smoke

The release of smoke-derived volatile phenols during the fermentation of Merlot grapes, following grapevine exposure to smoke, has been investigated. The concentrations of guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, and eugenol were determined by gas chromatography-mass spectrometry and found to increase throughout the winemaking process. Only trace levels (< or = 1 microg/L) of guaiacol and 4-methylguaiacol could be detected in free run juice derived from the fruit of smoked vines; the highest levels, 388 microg/L and 93 microg/L, respectively, were observed in the finished wine. Control wine (derived from fruit of unsmoked vines) contained 4 microg/L guaiacol, with the volatile phenols either not detected or detected at only trace levels (< or = 1 microg/L) throughout fermentation. The role of enzyme and acid catalyzed hydrolysis reactions in releasing smoke-derived volatile compounds was also investigated. The volatile phenols were released from smoked free run juice by strong acid hydrolysis (pH 1.0) and enzyme (beta-glucosidase) hydrolysis, but not mild acid hydrolysis (juice pH 3.2-3.7). Guaiacol was again the most abundant smoke-derived phenol, present at 431 microg/L and 325 microg/L in strong acid and enzyme hydrolysates, respectively. Only trace levels of each phenol could be detected in each control hydrolysate. This study demonstrates the potential for under-estimation of smoke taint in fruit and juice samples; the implications for the assessment of smoke taint and quantification of volatile phenols are discussed.     

Comparative study on phenolic content and antioxidant activity during maturation of the olive cultivar Chemlali from Tunisia

For the first time the identification and quantification of phenolic compounds of the Olea europaea L. cv. Chemlali olive were carried out to examine their profile during maturation. The phenolic composition was studied by using reverse-phase high-performance liquid chromatography during all steps of fruit development. Oleuropein is the abundant phenolic compound in Chemlali olive, and its concentration increases during maturation. An indirect relationship between oleuropein content in olive fruit and hydroxytyrosol was observed. Weak changes in the amounts of the other phenolic monomers and flavonoids were also observed. The total phenolic content varied from 6 to 16 g/kg expressed as pyrogallol equivalents. Its highest level was found at the last maturation period. The antioxidant capacity of olive extracts was evaluated by measuring the radical scavenging effect on 1,1-diphenyl-2-picrylhydrazyl. The IC(50) values of the olive extract ranged from 3.2 to 1.5 microg/mL. There was a correlation between antioxidant activity and total phenolic content of samples. The antioxidant activity increased with maturation. This could be attributed to the increase of the tolal phenol level with fruit development.     

Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoic Acid (PFOA) in Water Environment of Singapore

Recently, there has been increasing concern about perfluorinated compounds, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) due to their biotic and abiotic persistence and chronic toxicity. To characterize the spatial distribution and seasonal variation of PFOS and PFOA in the aquatic and oceanic environment of Singapore, more than 100 water samples from reservoirs, rivers/canals, coastal waters, and treated effluents of wastewater treatment plants (WWTPs) were collected and analyzed in this study. Solid-phase extraction followed by high-performance liquid chromatography (HPLC) coupled with tandem MS (HPLC/MS/MS) was applied to quantitatively identify PFOS and PFOA. PFOS concentrations in surface waters, wastewaters and coastal waters were in the range of 2.2?C87.3 ng/L, 5.8?C532 ng/L, and 1.9?C8.9 ng/L, respectively, while those of PFOA were 5.7?C91.5 ng/L, 7.9?C1,060 ng/L, 2.4?C17.8 ng/L, respectively. Compared with surface waters and wastewaters, coastal waters had lower concentrations of PFOS and PFOA. Highest concentration of PFOA (532 ng/L) and PFOA (1,060 ng/L) were observed in treated effluents of two WWTPs. Our results suggest that coastal waters in the western area of Singapore are more heavily contaminated than those in the middle and eastern areas. The release of effluents from WWTPs is an important pathway by which perfluorinated compounds enter the oceanic environment. Between dry season and wet season, significant seasonal differences (p?=?0.025) were observed in surface waters for PFOS only, while no discernable seasonal differences were found for both PFOS and PFOA in coastal waters and wastewaters.     

Oxidative transformation of natural and synthetic phenolic mixtures by Trametes versicolor laccase

The efficiency of Trametes versicolor laccase in the transformation of phenols (caffeic acid, catechol, hydroxytyrosol, methylcatechol, protocatechuic acid, syringic acid, m-tyrosol, 3-hydroxybenzoic acid, 3-hydroxyphenylacetic acid, 2,6-dihydroxybenzoic acid, 4-hydroxybenzaldehyde) usually present in waste water, such as that derived from an olive oil factory, was investigated. According to their response to 24 h laccase action the 11 phenolic compounds were classified in three groups: reactive (88-100% transformation), intermediate reactive (transformation lower than 50%), and recalcitrant (not transformed at all). The enzyme was able to transform the 11 substrates even when they were present in a mixture and also toward a phenolic extract from a Moroccan olive oil mill waste water (OMW) sample. The disappearance of protocatechuic, 3-hydroxyphenylacetic, and 2,6-dihydroxybenzoic acids, and 4-hydroxybenzaldehyde was enhanced whereas that of caffeic acid and m-tyrosol was depressed when the phenols were present in the mixture. A reduction of enzyme activity occurred in single and/or complex phenolic mixtures after enzymatic oxidation. No correspondence between phenol transformation and disappearance of enzymatic activity was, however, observed. The overall results suggest that laccases are effective in the transformation of simple and complex phenolic mixtures.     

Evaluation of the influence of thermal oxidation on the phenolic composition and on the antioxidant activity of extra-virgin olive oils

A comparison between the results obtained by using HPLC-UV, HPLC-MS, and CE-UV for characterizing the deterioration of extra-virgin olive oil during heating (180 degrees C) was investigated, taking into account phenolic compounds. The concentration of several compounds belonging to four families of phenols (simple phenols, lignans, complex phenols, and phenolic acids) was determined in the samples after the thermal treatment by all three techniques. Hydroxytyrosol, elenolic acid, decarboxymethyl oleuropein aglycon, and oleuropein aglycon reduced their concentration with the thermal treatment more quickly than other phenolic compounds present in olive oil. HYTY-Ac and Lig Agl were demonstrated to be quite resistant to this kind of treatment, and the behavior of lignans could be outstanding, as they belong to the family most resistant to thermal treatment. Several "unknown" compounds were determined in the phenolic profiles of the oils after the thermal treatment, and their presence was confirmed in refined olive oils. The oxidative stability index (OSI time) was reduced from 25 to 5 h after 3 h of heating, whereas the peroxide value showed a minimum after 1 h of heating.     

SEASONAL PATTERN OF WATER-SOLUBLE CONSTITUENTS FROM LEAVES OF POPULUS×'NORTHWEST' (HORT.)

Aqueous leaf extracts were obtained at regular intervals during the 1967 growing season from PopulusבNorthwest’ (Hort.). After lyophilization the samples were analysed for acidity and ash, sugar, phenol, and N contents. They were examined with thin-layer chromatography and infra-red spectroscopy. Simple phenolic compounds, present earlier in the growing season, made way for more complex phenols as the season progressed, and the extracted material became more acid. The increased loss of phenolic compounds and acids from the leaves toward the end of the summer continued during their first autumn on the ground. The polysaccharide content decreased during the season. The infra-red spectra of the lyophilized material were useful in making comparisons. It was concluded that, for percolation and transformation studies of Chemozemic soils, aqueous leaf extracts obtained during late summer or autumn should be the most relevant.     

酸法提取青稞麸皮结合酚工艺优化

为了提高青稞的附加利用价值,该文以青稞麸皮为研究对象,考察了提取试剂、酸质量分数、萃取pH值、料液比和提取温度对多酚质量分数和 DPPH·自由基清除能力的影响。采用中心组合设计优化其结合酚提取工艺。结果表明,青稞结合酚提取最优工艺条件为：提取试剂为硫酸,酸质量分数为11.10%,水料比为1：17 g/mL,提取温度为75℃,pH值不作处理,此条件下提取得到的结合酚质量分数达224.33 mg/(100 g),DPPH·自由基清除能力达9919.28μmol/(100 g),与预测值多酚质量分数243.80 mg/(100 g),其DPPH·自由基清除能力9087.02μmol/(100 g)基本一致。高效液相色谱法检测到最优工艺下所得青稞结合酚中含有8种酚酸及8种黄酮类物质,总量达325.104 mg/(100 g)。研究结果为全面评价青稞结合酚含量及青稞麸皮的高效利用提供科学依据。     

Water-soluble phenolic substances in soils under several coniferous and deciduous tree species

The humus layer of soils under Betula pendula, Quercus robur, Fagus sylvatica, Pinus nigra and Picea abies was analyzed for water-soluble phenolic substances. Highest concentrations of total water-soluble phenols were found in soils supporting oak trees. Highest polyphenol concentrations occurred under spruce-fir and beech trees, whereas highest monomeric phenols were found in soils under spruce-fir and pine. The polyphenol content was positively correlated with total carbon content of the soil. The phenolic acid composition of the soils under trees was partly dependent on the tree species. Among the monomeric compounds, ferulic, p-coumaric, vanillic, protocatechuic, syringic and benzoic acid dominated the phenol spectra.Seasonal variations were observed in the concentrations of water-soluble and mild alkaline-soluble phenols in the humus layer under F. sylvatica in two contrasting soil types. The water-soluble phenols in a sandy soil accounted for a larger proportion of the mild-alkaline extractable amounts compared to a loamy soil.     

Analysis of pesticide residues by chemical derivatization. II. N-methylcarbamates in natural water and soils.

A method for the quantitative determination of several N-methylcarbamates in natural waters and the applicability of the derivative to soil samples using a previously published extraction procedure are described. After extraction of the carbamates from the substrate, the carbamates are hydrolyzed in a 10% methanol-potassium hydroxide solution to form the phenolic hydrolysis products, which are isolated and derivatized with pentafluorobenzyl (PFB) bromide to produce the PFB ether derivatives. The PFB derivatives are cleaned up and fractionated on a silica gel microcolumn and determined by electron capture gas-liquid chromatography (GLC). Eight organophosphate pesticides and 2 phthalate acid esters that hydrolyze to phenols or phthalic acid were evaluated as potential interferences and were found not to interfere with any of the carbamates tested. Quantitative determinations of 0.1 mug carbofuran and 3-ketocarbofuran and 0.5 mug carbaryl, metmercapturon, and Mobam in a 1 L water sample are possible. Propoxur was not determined at levels less than 1 mug/L due to the short GLC retention time of the derivative and interferences from the reagents at the lower levels.     

Effect of solvent, temperature, and solvent-to-solid ratio on the total phenolic content and antiradical activity of extracts from different components of grape pomace

Grape byproducts were subjected to an extraction process under various different experimental conditions (namely, solvent type, temperature, solvent-to-solid ratio, time contact, and raw material) in order to study the effect of these conditions on the yield of phenolic compounds and the corresponding antiradical activity of extracts. Although the order of decreasing capacity to extract soluble materials was ethanol > methanol > water, methanol was the most selective for extracting phenolic compounds. Temperature and solvent-to-solid ratio were found to have a critical role in extraction efficiency; values of 50 degrees C (between 25 and 50 degrees C) and 1:1 (between 1:1 and 5:1) maximized the antiradical activity of phenolic extracts. In addition, extracts from grape samples previously subjected to distillation reached higher antiradical values in comparison to those coming directly from pressing; in both cases, seed extracts showed better results than those of stem when ethanol or water was employed, whereas the opposite occurred in the case of methanol. These differences were attributed to the different phenolic compositions of the considered fractions.