Evaluation of pharmaceuticals and personal care products as water-soluble molecular markers of sewage

We examined the utility of 13 pharmaceuticals and personal care products (PPCPs) as molecular markers of sewage contamination in riverine, groundwater, and coastal environments. The PPCPs were crotamiton, ibuprofen, naproxen, ketoprofen, fenoprofen, mefenamic acid, thymol, triclosan, propyphenazone, carbamazepine, diethyltoluamide, ethenzamide, and caffeine. Measurements in 37 Japanese rivers showed positive correlations of riverine flux of crotamiton (r2 = 0.85), carbamazepine (r2 = 0.84), ibuprofen (r2 = 0.73), and mefenamic acid (r2 = 0.67) with the population in the catchments. In three surveys in the Tamagawa estuary, crotamiton, carbamazepine, and mefenamic acid behaved conservatively across seasons within a salinity range of 0.4-29 per thousand, suggesting their utility as molecular markers in coastal environments. Removal of ketoprofen and naproxen in the estuary was ascribed to photodegradation. Ibuprofen and thymol were removed from estuarine waters in summer by microbial degradation. Triclosan was removed by a combination of microbial degradation, photodegradation, and adsorption. These results were consistent with those of river water incubated for 8 d at 25 degrees C in the dark in order to examine the effects of biodegradation and photodegradation. Crotamiton was detected in groundwater from the Tokyo metropolitan area (12 out of 14 samples), suggesting wastewater leakage from decrepit sewers. Carbamazepine, ketoprofen, and ibuprofen (5/14), caffeine (4/14), and diethyltoluamide (3/14) were also detected in the groundwater, whereas the other carboxylic and phenolic PPCPs were not detected and were thought to be removed during their passage through soil. All the data demonstrated the utility of crotamiton and carbamazepine as conservative markers in freshwater and coastal environments. We recommend combining these conservative markers with labile PPCPs to detect inputs of poorly treated sewage.     

Fluorescent whitening agents in Tokyo Bay and adjacent rivers: their application as anthropogenic molecular markers in coastal environments

Two kinds of stilbene-type fluorescent whitening agents (i.e., DSBP and DAS1), minor components of laundry detergents, were analyzed in surface waters of Tokyo Bay and adjacent rivers and in sewage effluents to examine their usefulness as molecular markers in the marine environment. Sensitive determination using HPLC (high performance liquid chromatography) with fluorescence detection with postcolumn UV radiator was employed. DSBP and DAS1 were found in Tokyo rivers at concentrations of a few microg/L and approximately 1 microg/L, respectively. DSBP and DAS1 were widely distributed in Tokyo Bay waters at concentrations in the range of 0.019-0.264 microg/L and 0.021-0.127 microg/L, respectively. Comparison of these concentrations with those in sewage effluents (DSBP: 8 microg/L and DAS1: 2.5 microg/L on average) yielded sewage dilutions in Tokyo Bay on the order of 10(2). FWAs-salinity diagram in the Tamagawa Estuary showed fairly conservative behaviors of the FWAs with approximately 20% and approximately 10% removal of DSBP and DAS1, respectively. This is thought to be caused by photodegradation. The persistent nature of FWAs and their widespread distribution in coastal environments demonstrates the utility of FWAs in tracing the behavior of water from rivers and sewage outfalls. The DSBP/DAS1 ratio showed a decreasing trend from sewage effluents, to rivers, to Tokyo Bay, indicating selective photodegradation of DSBP. The DSBP/DAS1 ratio is proposed as an index of the degree of photodegradation and residence time and freshness of water mass in coastal environments.     

低反式脂肪酸氢化油脂研究进展

综述了油脂氢化制备低反式脂肪酸氢化油脂工艺的最新研究进展.介绍了电化学催化氢化和超临界氢化的反应原理、反应器构造及工艺参数对氢化反应的影响,并分别阐述了其与传统油脂氢化、贵金属催化氢化相比在制备低反式脂肪酸氢化油脂方面的优缺点.     

Evaluation of three different molecular markers for the detection of Staphylococcus aureus by polymerase chain reaction

The aim of this study was to target three genes of Staphylococcus aureus-fmhA (coding for a factor of unknown function), catalase and femA (coding for a factor essential for methicillin resistance) to establish and validate a PCR assay for the detection of this pathogen. Two pairs of primers were designed for fmhA and one pair each for catalase and femA genes. The PCR assays were standardized and found to give specific amplicons under similar reaction parameters. Target specificity of the primers was confirmed by DNA sequencing of the amplicons. While the initial inclusivity and exclusivity test reactions were in agreement in case of three of the primer pairs, one pair based on fmhA gene produced a non-specific product with a template DNA used in exclusivity test reactions. Forty-five strains of S. aureus were subjected to these PCR assays for their evaluation. Three among the four pairs of primers, one against each gene detected all the 45 strains precisely whereas one of the PCR assays using primers targeting the fmhA gene did not generate the specific amplicon with several of the strains. Seven unidentified strains of Gram-positive cocci subjected to these PCR assays produced negative results for each culture. Six of the strains were identified as Staphylococcus haemolyticus and one strain as Staphylococcus arlettae by 16S ribosomal gene analyses. All the three assay systems showed a detection limit of 100 cells per 20mul reaction assay. For validation of these assay systems, 80 coded samples of 11% skimmed milk spiked with different pathogens were received from NICED (National Institute of Cholera and Enteric Diseases), Kolkata and subjected to these PCR assays. All the three assays could detect S. aureus correctly in two of the samples. Amongst 150 raw milk samples, 36 (24%) were found positive for S. aureus. We conclude that fmhA, catalase and femA genes are conserved in S. aureus and, therefore, could be used as specific targets for its detection and identification by PCR. The protocols developed herein could be used for rapid and specific detection of this pathogen in food, clinical and environmental samples, especially milk.     

两种分子标识在酵母分子鉴定中的比较

rDNA序列同源性分析是一种通用的酵母分子鉴定方法,26S rDNA D1/D2区域和rDNA内部转录间隔区(Internal Transcribed Spacer,ITS)是rDNA序列同源性分析中最为常用的两种分子标识。同时使用这两种分子标识对20株分离自水果表面的酵母菌株进行分子鉴定,结果显示19株酵母分离物的鉴定结果相一致,两种分子标识序列在认定酵母种内和种间关系时都拥有足够的差异,能将大部分酵母菌株直接鉴定到种一级水平。     

Chitosan coating for the protection of amino acids that were entrapped within hydrogenated fat

A novel formulation method was suggested to prepare rumen-protected amino acid by coating chitosan on the particles of hydrogenated fat entrapping amino acid. Chitosan coating that was formed due to the coacervation either by the addition of ethanol or sodium hydroxide to the acetic acid solution of chitosan could increase the retention of amino acid in the fat prills. Both protected methionine and arginine particles showed a sustained release behavior in simulated rumen conditions. In the pH 5.5 buffer, the protected arginine particles coated with chitosan by the coacervation using NaOH could retain about 80% of arginine. When the coacervation with the addition of ethanol was employed, the chitosan-coated particles could retain even 97% of arginine. The chitosan-coated methionine particles prepared by addition of ethanol led to almost the same level (85%) of retention as the commercial product Mepron M85. Both the Higuchi kinetics and the model for the release of agent dissolved in polymer matrix could well describe the control release of protected amino acid.     

Oxidative conversion as a means of detecting precursors to perfluoroalkyl acids in urban runoff

A new method was developed to quantify concentrations of difficult-to-measure and unidentified precursors of perfluoroalkyl carboxylic (PFCA) and sulfonic (PFSA) acids in urban runoff. Samples were exposed to hydroxyl radicals generated by thermolysis of persulfate under basic pH conditions and perfluoroalkyl acid (PFAA) precursors were transformed to PFCAs of related perfluorinated chain length. By comparing PFCA concentrations before and after oxidation, the concentrations of total PFAA precursors were inferred. Analysis of 33 urban runoff samples collected from locations around the San Francisco Bay, CA indicated that PFOS (2.6-26 ng/L), PFOA (2.1-16 ng/L), and PFHxA (0.9-9.7 ng/L) were the predominant perfluorinated compounds detected prior to sample treatment. Following oxidative treatment, the total concentrations of PFCAs with 5-12 membered perfluoroalkyl chains increased by a median of 69%, or between 2.8 and 56 ng/L. Precursors that produced PFHxA and PFPeA upon oxidation were more prevalent in runoff samples than those that produced PFOA, despite lower concentrations of their corresponding perfluorinated acids prior to oxidation. Direct measurements of several common precursors to PFOS and PFOA (e.g., perfluorooctanesulfonamide and 8:2 fluorotelomer sulfonate) accounted for less than 25% of the observed increase in PFOA, which increased by a median value of 37%. Exposure of urban runoff to sunlight, advanced oxidation processes, or microbes could result in modest, but measurable, increases in concentrations of PFCAs and PFSAs.     

Quantitative determination of conjugated linoleic acids in hydrogenated vegetable oils using refractive index

Conjugated linoleic acid contents in hydrogenated vegetable oils were differentially determined using refractive indices when the iodine value could not be used. The refractive indices of soybean oil, cottonseed oil, and corn oil varied linearly with changes of linoleic acid contents of individual oils with determination coefficients of 0.91, 0.98, and 0.98, respectively. The refractive index can be used as a simple and fast method for control of the hydrogenation process of vegetable oils to obtain a desired conjugated linoleic acid content without fatty acid compositional analysis.     

气相色谱法测定氢化油脂加工食品中反式脂肪酸含量

目的建立气相色谱法测定氢化油脂加工食品中反式脂肪酸含量的分析方法。方法采用HP-88毛细管石英柱(30 m×0.25 mm×0.20μm)分离定性和定量43种饱和脂肪酸、不饱和脂肪酸,并应用于市售饼干、糕点、冰淇淋、奶茶、巧克力、咖啡等加工食品中的反式脂肪酸含量测定。结果顺、反式脂肪酸在30 m长的毛细管石英柱分离情况良好,各反式脂肪酸在3~100μg/m L浓度范围内TFA线性良好(R≥0.9990),重现性好(RSD6%),回收率85.3%~91.8%,检测限为0.01 g/100 g;其分离速度较100 m长的毛细管石英柱提高了1倍;奶油蛋糕、炼奶起士、饼干类含有的反式脂肪酸含量较高,且以反式棕榈油酸(t-C16:1)、反式油酸(t-C18:1)为主。结论该方法快速、准确、分离良好,可作为检测氢化油脂加工食品中反式脂肪酸含量的推广方法。     

Characterisation and evaluation of humic acids extracted from urban waste as liquid fertilisers

In this work a comparative study of humic acids extracted from organic wastes (sewage sludge and compost) and those currently used in the humic acid companies (humic acids from leonardite and peat) was carried out. Humic acids were characterised by means of chemical analysis (elemental and functional analysis) and spectroscopic techniques (¹³C NMR, gel filtration and infrared spectra) in order to relate their characteristics with their effect on plant growth. Chemical and spectroscopic analysis emphasised the different nature of the studied humic acids. The humic acids derived from the less evolved organic materials (sludge and compost) showed higher aliphatic nature, higher nitrogen compound content, lower oxidation degree and more heterogeneous composition than those extracted from more evolved materials (peat and leonardite). However, all these differences did not lead to significant differences in plant growth, but all these humic acids showed an increase of the yield respect to the control. ©1997 SCI     

谷子分子标记研究与应用

谷子是我国传统粮食作物,具有抗旱、耐瘠薄、营养价值高等优点,谷子的种质资源分析及育种研究非常重要,随着分子生物学的发展,分子标记技术的出现为谷子的遗传研究及育种开辟了新的思路和手段。分子标记包括DNA分子标记和蛋白质分子标记,其中DNA分子标记常被用于构建遗传连锁图谱、基因定位及QTL分析、遗传多样性研究、系谱分析与品种鉴定和比较基因组研究等,本文分别介绍了谷子常用的DNA分子标记和蛋白质分子标记及其特点,并综述了其在谷子上的研究应用情况,简要分析和展望了分子标记在谷子上的未来发展。     

毛细管气相色谱法测定精炼和氢化大豆油中的反式脂肪酸

采用CP—Sil88强极性毛细管柱气相色谱法对精炼和氢化大豆油中的顺、反异构和位置异构的脂肪酸进行定性、定量分析。结果表明，精炼和氢化大豆油中主要顺、反式脂肪酸实现了很好地分离，各种位置异构的反式脂肪酸也实现了较好地分离。采用归一化法对各种脂肪酸进行定量分析，结果表明，精炼大豆油中反式脂肪酸为总脂肪酸含量的3．45％，以△9c，12t—C18：2、△9t，12c—C18：2和△9c，12c，15t—C18：3、△9t，12c，15c—C18：3 4种形式为主；氢化大豆油中反式脂肪酸为总脂肪酸含量的38．73％，以△9t—C18：1、△10t—C18：1、△11t—C18：1 3种形式为主的反式十八碳单烯酸（t—C18：1）占反式脂肪酸总量的90．81％。     

Evaluation of the adsorption behavior of flavonoids and phenolic acids onto a food-grade resin using a D-optimal design

A D-optimal experimental design has been applied to study the single-compound adsorption of caffeic acid, catechin, chlorogenic acid, and phloridzin from aqueous solutions onto a food-grade styrene–divinylbenzene copolymer. Among the parameters determining adsorption the solute concentration, the temperature, the pH value, and the resin amounts were evaluated. Mathematical models were established for each phenolic compound allowing to predict the adsorption behavior under any given condition. Furthermore, determination of the optimal adsorption conditions using the mathematical equations was possible, thus facilitating systematic optimization of the adsorption process. The Langmuir and Freundlich isotherms have been applied to describe the adsorption of the four phenolic compounds and were used to interpret the adsorption behavior. Finally, ΔG, ΔH and ΔS were determined to evaluate polyphenol adsorption based on thermodynamic parameters. The present study contributes to optimize adsorber technology, thus, being a prerequisite for establishing cost-efficient technological processes for the recovery of plant phenolic compounds.     

Analysis and formation of trans fatty acids in hydrogenated soybean oil during heating

Hydrogenated oil has been widely used for production of shortenings or margarine, however, the presence of trans fatty acids may be detrimental to human health. The objectives of this study were to develop an improved method for analysis of trans fatty acids and evaluate their formation in both unhydrogenated and hydrogenated soybean oil during heating at 160, 180 and 200 °C for varied length of time. Results showed that among the four columns tested, an Agilent HP-88 column (100 × 0.25 mm I.D., 0.2-μm film thickness) could resolve eight trans fatty acids and nine cis fatty acids simultaneously within 31 min with injector temperature 240 °C, detector temperature 250 °C, and column temperature 170 °C in the beginning, maintained for 24 min, increased to 220 °C at 7.5 °C/min, 230 °C at 10 °C/min, and maintained for 5 min. The contents of both cis and trans fatty acids showed a decreased trend for the increase of heating time or temperature. No trans fatty acid formation was observed even after extensive heating of unhydrogenated and hydrogenated soybean oil for 24 h. This phenomenon demonstrated that trans fatty acids can only be formed under severe conditions.     

Benzothiazolamines as tire-derived molecular markers: sorptive behavior in street runoff and application to source apportioning

Wash-off and sorptive behaviors of two benzothiazolamines (BTs) [i.e., 2-(4-morpholinyl)benzothiazole (24MoBT) and N-cyclohexyl-2-benzothiazolamine (NCBA)] have been investigated as possible molecular markersfortire debris and/or road dust transported in highway runoff water. Sum of dissolved and particulate 24MoBT and NCBA concentrations in runoff water ranged from 15 to 417ng/L and from 22to 508ng/L, respectively. Proportions of NCBA in particulate (>0.7microm) phase (<9-79%) were larger than that of 24MoBT (<1-14%), which was consistent with their experimentally determined octanol/water partition coefficients (Kow; 10(4.23+/-0.14) for NCBA; 10(2.42+/-0.03) for 24MoBT). The organic carbon-normalized in-situ partition coefficient (Koc') observed in runoff events (10(4.69+/-0.28) for NCBA; 10(3.42+/-0.23) for 24MoBT) were 1 order of magnitude higher than those expected from their Kow, indicating strong affinity of BTs to suspended particulate matter (SPM) in runoff water. Furthermore, in desorption experiments lasting 24 h, we observed almost the same levels of Koc' as those in runoff events, implying that significant fractions of BTs are strongly associated with runoff particles and not easily available to equilibrium partitioning. NCBA was ubiquitous in sediments from the Nogawa River receiving runoff from the Chuo Highway, whereas many of those samples had undetectable levels of 24MoBT. All of above results indicate that NCBA would be more suitable than 24MoBT as a molecular marker for runoff particles loading the aquatic environment. By using SPM-weighted mean concentration of particulate NCBA, at least 3.3+/-1.6% of the mass in the Nogawa sediments is estimated to be from runoff SPM.     

Isomeric distribution and rapid determination of trans-octadecenoic acids in German brands of partially hydrogenated edible fats

The determination of trans fatty acids (TFA), in particular trans-octadecenoic acids, in edible fats is of current interest, since just in the last years a variety of negative physiological effects has been related to TFA. A main source of C18:1 trans fatty acids are partially hydrogenated fats. Besides the total content of trans-octadecenoic acids, their isomeric distribution seems to be even more important, as fats of different origin, e.g. partially hydrogenated fats and ruminant fats, possibly show different physiological properties. In this study, 46 margarines and 16 shortenings and cooking fats, purchased in August of 1994, were analyzed for trans-octadecenoic acid isomers by a two-step method (Ag-TLC/HRGC). The mean relative isomeric distributions (g/100 g TFA) of both groups determined with a 100 m-column were comparable, with Δ9 and Δ10 being the main isomers. By repeated analysis of 15 brands between August of 1994 and January of 1996, the mean total C18:1 TFA content was found to have decreased in these margarines (n = 8) from 9.58% to 4.62% but not in shortenings/cooking fats (n = 7; 11.62% to 11.92%). The relative isomeric distribution was not affected in both groups. To avoid the problem of overlaps between cis-and trans-C18:1 isomers with GC analysis, formulae for the rapid determination of total C18:1 TFA contents in margarines and shortenings/cooking fats from direct GC data were statistically derived. Thus, applying these formulae and considering the mean relative distributions, absolute contents of all individual isomers of trans-octadecenoic acids can rapidly be determined from direct GC.     

两种Pricat镍催化剂对大豆油氢化中固脂和反式酸含量的影响

研究了两种Prieat镍催化刺在大豆油氢化过程中对固脂和反式酸含量的影响。结果表明，9908型催化荆适合油脂的选择性氢化，而9910型则适合植物油的极度氢化。详细探讨了9908型催化刺在不同氢化温度、氢气压力以及催化荆浓度下对氢化油固体脂肪含量以及反式脂肪酸的影响。结果表明，温度对氢化反应的异构化影响较大，氢气压力和催化剂浓度对异构化的影响相对较小。     

Hydroxydicarboxylic acids: markers for secondary organic aerosol from the photooxidation of alpha-pinene

Detailed organic analysis of fine (PM2.5) rural aerosol collected during summer at K-puszta, Hungary from a mixed deciduous/coniferous forest site shows the presence of polar oxygenated compounds that are also formed in laboratory irradiated alpha-pinene/NOx/air mixtures. In the present work, two major photooxidation products of alpha-pinene were characterized as the hydroxydicarboxylic acids, 3-hydroxyglutaric acid, and 2-hydroxy-4-isopropyladipic acid, based on chemical, chromatographic, and mass spectral data. Different types of volatile derivatives, including trimethylsilyl ester/ether, methyl ester trimethylsilyl ether, and ethyl ester trimethylsilyl ether derivatives were measured by gas chromatography/mass spectrometry (GC/MS), and their electron ionization (El) spectra were interpreted in detail. The proposed structures of the hydroxydicarboxylic acids were confirmed or supported with reference compounds. 2-Hydroxy-4-isopropyladipic acid formally corresponds to a further reaction product of pinic acid involving addition of a molecule of water and opening of the dimethylcyclobutane ring; this proposal is supported by a laboratory irradiation experiment with alpha-pinene/NOJ0 air. In addition, we report the presence of a structurally related minor alpha-pinene photooxidation product, which was tentatively identified as the C7 homolog of 3-hydroxyglutaric acid, 3-hydroxy-4,4-dimethylglutaric acid. The detection of 2-hydroxy-4-isopropyladipic acid in ambient aerosol provides an explanation for the relatively low atmospheric concentrations of pinic acid found during daytime in forest environments.     

谷子SSR分子标记的研究进展

谷子作为一种在中国杂粮作物中占据重要地位的粮食作物,其全基因组测序的完成极大地促进了谷子分子标记技术的发展。SSR作为第二代分子标记,具有操作简单、重复性好、结果可靠等优势,现已被广泛应用于作物遗传多样性、遗传连锁图谱构建、数量性状分析、品种鉴定等研究。文章对SSR标记技术在谷子遗传多样性、遗传连锁图谱等方面的研究进行综述,以期为中国谷子SSR标记技术发展提供参考与借鉴。     

Evaluation of ISSR markers for genetic diversity analysis in Anatolian water buffaloes

BACKGROUND: The utilisation of molecular markers has increased in molecular research recently. Inter‐simple sequence repeat (ISSR) markers allow the analysis of genomes without preliminary sequence information, since random primers are used. The purpose of the present study was to evaluate ISSR markers for assessing the genetic diversity of indigenous Anatolian Water Buffaloes reared in Afyon, Konya and Sivas provinces of Turkey, with a view to conservation of the gene resources. RESULTS: The 11 ISSR primers chosen for the analysis revealed a total of 110 bands, of which 76 (69.09%) were polymorphic. Also, genetic similarity, polymorphic information content (PIC), resolving power (R_p) and mean resolving power (R_p ), heterozygosity (H) and Shannon index (I) were calculated as 0.9479–0.9562, 0.35 ± 0.20, 2.73, 0.27, 0.18 ± 0.07 and 0.28 ± 0.11, respectively. CONCLUSION: The ISSR markers were found to be promising for assessing the genetic diversity in buffalo populations. Potential genetic parameters such as PIC, R_p, R_p , H and I were effectively used in this study. Copyright © 2011 Society of Chemical Industry