一株壬基酚降解菌的分离鉴定及其对壬基酚同分异构体降解特性研究

壬基酚(NP)是典型的内分泌干扰物,具有雌激素效应.目前对NP的研究主要集中于微生物降解对其整体去除效果,而对各NP同分异构体的降解行为尚缺乏系统性研究.从钱塘江沉积物中筛选得到一株能够降解NP的细菌,命名为N-1,实验室条件下该菌能以NP为唯一碳源生长.经形态、生理生化及16S rRNA基因序列分析,N-1鉴定为假黄单胞菌(Pseudoxanthomonas sp.).通过正交试验确定N-1降解NP的最适条件为:温度30℃,p H=7.0,菌量10%,NP浓度5~10 mg·L~(-1).最适条件下,N-1对NP 16 d整体降解率可达88.0%,对10种NP异构体降解率在69.7%~100%之间,说明N-1对NP同分异构体的降解具有结构-降解特性,即不同结构NP异构体表现出不一样的降解能力.进一步研究发现,NP异构体降解率随着NP烷基C链长度增加而升高,随着烷基取代基结构越复杂而降低.NP降解选择性导致的难降解成分残留现象,为NP类异构体污染物的微生物修复提供了一定的理论依据.     

Effects of a catalytic converter on PCDD/F, chlorophenol and PAH emissions in residential wood combustion

Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hisida), minke whale (Balaenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984-2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9-C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006.     

Effect of maternal dietary hexachlorocyclohexane exposure on pup survival and growth in albino rats

Abstract

In adult albino rats, maternal dietary. ß‐ and ?‐hexachlorocyclohexane (HCH) intake during gestation upto 400 ppm level did not affect the number of litters produced. But about 50 and 100% pup mortality was found in 200 and 400 ppm ß ‐HCH group within 5 days of birth. Maternal mortality was observed in 800 ppm ß ‐HCH group during third week of gestation. The effect of maternal dietary intake of HCH isomers at 50 and 250 ppm level during gestation and/or lactation on perinatal development was also studied. The body weights and sizes of the newborn litters of mother rats exposed to dietary HCH isomers did not. differ from controls. Similarly, the growth and development of the litters of HCH exposed mother rats that survived 28 day lactation period were found to be comparable to controls as evidenced by the body weight and weight of vital organs. However, liver weight increases were found in the 28 day weaned litters wherever the mothers had been exposed to HCH isomers during lactation. Lowered kidney weight was seen in litters of mother rats fed 250 ppm ?‐HCH during gestation and lactation. The brain and testis weights were not affected in the litters of any experimental groups.     

Gas chromatographic separation and determination of chloroanthracene isomers on fly ash

An efficient, reproducible and rapid fused silica capillary column gas chromatographic method, in splitless mode, for analysing of the three chloroanthracene isomers is described. The method affords efficient separation and good linearity for each isomer in the range of 0.2 -200 μg/ml. The method can also be used in separation and determination of another thirty three aromatic and their halosubstituted compounds. This paper also presents the applications of the method in analysing of complex products mixture from reaction of the selected aromatic compounds with hydrogen chloride on fly ash surface from municipal incinerator.     

Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

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.     

Distribution and health risk assessment of organochlorine pesticides （OCPs） in industrial site soils： A case study of urban renewal in Beijing, China

A field survey was conducted in a contaminated industrial site of southern Beijing,China to investigate the contents and distribution of the organochlorine pesticides(α-,β-,γ-,δ-HCH,p,p-DDT,p,p-DDE,p,p-DDD and o,p-DDT) in the profiles of soil,and a health risk assessment was carried out with CalTOX multimedia exposure model.Results showed that mean concentrations of total hexachlorocyclohexane isomers(HCHs) and total dichlorodiphenyltrichloroethane isomers(DDXs) in soils were in the range of 13.20-148.71 mg...     

Linear and branched perfluorooctane sulfonate (PFOS) isomer patterns differ among several tissues and blood of polar bears

Perfluorooctane sulfonate (PFOS) is a globally distributed persistent organic pollutant that has been found to bioaccumulate and biomagnify in aquatic food webs. Although principally in its linear isomeric configuration, 21–35% of the PFOS manufactured via electrochemical fluorination is produced as a branched structural isomer. PFOS isomer patterns were investigated in multiple tissues of polar bears (Ursus maritimus) from East Greenland. The liver (n = 9), blood (n = 19), brain (n = 16), muscle (n = 5), and adipose (n = 5) were analyzed for linear PFOS (n-PFOS), as well as multiple mono- and di-trifluoromethyl-substituted branched isomers. n-PFOS accounted for 93.0 ± 0.5% of Σ-PFOS isomer concentrations in the liver, whereas the proportion was significantly lower (p < 0.05) in the blood (85.4 ± 0.5%). Branched isomers were quantifiable in the liver and blood, but not in the brain, muscle, or adipose. In both the liver and blood, 6-perfluoromethylheptane sulfonate (P6MHpS) was the dominant branched isomer (2.61 ± 0.10%, and 3.26 ± 0.13% of Σ-PFOS concentrations, respectively). No di-trifluoromethyl-substituted isomers were detectable in any of the tissues analyzed. These tissue-specific isomer patterns suggest isomer-specific pharmacokinetics, perhaps due to differences in protein affinities, and thus differences in protein interactions, as well transport, absorption, and/or metabolism in the body.     

Distribution pathways of hexachlorocyclohexane isomers in a soil-plant-air system. A case study with Cynara scolymus L. and Erica sp. plants grown in a contaminated site

This study focuses on the main routes of distribution and accumulation of different hexachlorocyclohexane (HCH) isomers (mainly α-, β-, γ- and δ-HCH) in a soil-plant-air system. A field assay was carried out with two plant species, Cynara scolymus L. and Erica sp., which were planted either: (i) directly in the HCH-contaminated soil; or (ii) in pots filled with uncontaminated soil, which were placed in the HCH-contaminated soil. Both plant species accumulated HCH in their tissues, with relatively higher accumulation in above-ground biomass than in roots. The β-HCH isomer was the main isomer in all plant tissues. Adsorption of HCH by the roots from contaminated soil (soil → root pathway) and adsorption through the aerial biomass from either the surrounding air, following volatilization of the contaminant (soil → air → shoot pathway), and/or contact with air-suspended particles contaminated with HCH (soil particles → shoot pathway) were the main mechanisms of accumulation. These results may have important implications for the use of plants for reducing the transfer of contaminants via the atmosphere.     

Determination of alcohol compounds using corona discharge ion mobility spectrometry

Ion mobility spectrometry （IMS） is a very fast, highly sensitive, and inexpensive technique, it permits efficient monitoring of volatile organic compounds like alcohols. In this article, positive ion mobility spectra for six alcohol organic compounds have been systematically studied for the first time using a high-resolution IMS apparatus equipped with a discharge ionization source. Utilizing protonated water cluster ions （H2O）nH^＋ as the reactant ions and clean air as the drift gas, alcohol organic compounds, ethanol, 1- propanol, 2-propanol, 1-butanol, 1-pentanol and 2-octanol, all exhibit product ion characteristic peaks in their respective ion mobility spectrometry, that is a result of proton transfer reactions between the alcohols and reaction ions （H2O）nH^＋. The mixture of these alcohols, including two isomers, has been detected, and the results showed that they could be distinguished effectively in the ion mobility spectrum. The reduced mobility values have been determined, which are in very well agreement with the traditional ^63Ni-IMS experimental values. The exponential dilution method was used to calibrate the alcohol concentrations, and a detection limit available for the alcohols is in order of magnitude of a few ng/L.