O3/H2O2降解Atrazine效能研究

利用O3/H2O2降解莠去津,对氧化产物进行了色谱分析,以评价该体系降解莠去津效能.莠去津初始浓度2 mg/L,7.5mg/L的O3单独氧化去除率为27.2%;相同O3投量下,H2O2/O3摩尔比0.75时,5 min莠去津的去除率最高可达96.5%,表明H2O2/O3体系对莠去津的去除效果良好,降解速度快.以离子色谱对产物的离子进行分析,莠去津浓度下降的同时,硝酸根和氯离子浓度增高.GC-MS检测的产物和对LC-MS谱图的分析表明,有机产物中存在脱乙基、脱异丙基和脱氯莠去津,说明H2O2/O3并不能彻底氧化莠去津,因此工程中作为主要去除单元或突发性污染事件的应急手段可能还需要与活性炭等单元联用.     

Diminution of migration of phthalic acid esters in tequila beverage by the year of production

Abstract

The presence of diethyl-phthalate (DEP), dibutyl-phthalate (DBP), butylbenzyl-phthalate (BBP), diethylhexyl-phthalate (DEHP) and diisononyl-phthalate (DINP) was determined in 295 tequila samples. They were grouped by age of maturation (white, aged, extra aged or ultra aged) and year of production (between 2013 and 2018). Gas Chromatography coupled with Mass Spectrometry was used for identification and quantification. The results showed that 65 samples (22% of the total) were phthalate free. DEP (0.13-0.27?mg/kg), BBP (0.05–2.91?mg/kg) and DINP (1.64–3.43?mg/kg) were detected in 11 (3.73%), 37 (12.54%) and 5 (1.69%) samples, respectively. But, these concentrations did not exceed the maximum permitted limits (MPL) of phthalates for alcoholic beverages. DBP (0.01–2.20?mg/kg) and DEHP (0.03–4.64?mg/kg) were detected in 96 (32.54%) and 224 (75.93%) samples, from them only 10 (3.39%) and 15 (5.08%) samples, respectively, exceeded the MPL for alcoholic beverages and they were few tequilas produced in the year 2014 or before. DEHP was the most frequent phthalate found in tequila and observed DEHP concentrations were 2-times higher in ultra aged tequilas compared to those in white tequilas. We concluded that all tequilas produced in 2015 and after, satisfied the international standards for these compounds.     

Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1 L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC–MS/MS and LC–MS/MS). Instrument detection limits ranged between 0.12–7.5 pg with corresponding method reporting limits of 1–10 ng l⁻¹ in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6–22%).     

The impact of pesticides on oxidative stress level in human organism and their activity as an endocrine disruptor

Pesticides cause serious environmental and health problems both to humans and animals. The aim of this review is to discuss selected herbicides and fungicides regarding their mode of action and their influence on basic oxidative stress parameters and endocrine disruption properties tested in selected cell cultures in vitro. Because of numerous difficulties which animal studies are subject to, cell cultures are an excellent experimental model reflecting human exposure to different pesticides through all relevant routes. This experimental model can be used to monitor aggregate and cumulative pesticide exposures.     

Endocrine disruption of water and sediment extracts in a non-radioactive dot blot/RNAse protection-assay using isolated hepatocytes of rainbow trout

Goal, Scope and Background In order to evaluate the estrogenic activity of sediments and XAD water extracts of selected sites of the catchment area of the River Neckar, a river system in Southern Germany, an integrative assessment approach was used to assess the ecological hazard potential of endocrine-disrupting compounds in sediment and water. Methods The approach is based on estrogen receptor-mediated vitellogenin synthesis induced in isolated hepatocytes of rainbow trout and quantified in a non-radioactive dot blot/RNAse protection-assay in parallel to comprehensive chemical analyses of estrogenic substances. Results and Discussion Numerous investigated extracts revealed an estrogen activity comparable to that of the positive control (1 nM 17?-estradiol corresponding to 270 ng/L in the test medium). Based on a concentration factor of 30 in the extracts and a recovery of XAD resins of approximately 80 %, 17?-estradiol equivalent concentrations between 20 and 26.7 ng/L could be calculated downstream of a sewage treatment plant (< 0.1 ng/L for a reference site). A comparison of the bioassay-derived Bio-TEQs (toxicity equivalents) and the Chem-TEQs revealed a high correlation with a Pearson coefficient of 0.85, indicating that the same ranking of the samples could be obtained with respect to the endocrine disrupting potential with both chemical and bioanalytical analysis. However, the TEQ concentrations computed from chemical analyses were significantly lower than the bioassay-derived TEQ concentrations. In fact, in none of the samples, more than 14 % of the vitellogenin-inducing potency could be attributed to the substances (steroids, alkylphenols, bisphenol A, diethylstilbestrol) analyzed. A comparison of the endocrine disrupting potential of sediments extracted by the solvents acetone and methanol revealed lower biological effects for acetone-extracted samples. Possible reasons may be a masking of endocrine effects in acetone extracts by cytotoxicity, a low extraction efficiency of the solvent acetone, or anti-estrogen potencies of some extracted sediment compounds. Using a mass balance approach, the contribution of the compounds analyzed chemically (Chem-TEQs) to the total endocrine activity (Bio-TEQs) was calculated. Based on the very low detection limits, particularly of the steroids with their high TEF factors, results revealed that a calculation of the Chem-TEQs is associated with considerable scale inaccuracy: Whereas only 7-15 % of the biological effectiveness (Bio-TEQs) could be explained by endocrine substances identified above the detection limits, the assumption of concentrations slightly below the given detection limits would result in a significant over estimation (137-197 %) of the Bio-TEQs. Even the interassay variation of the dot blot assay with different fish donors for primary hepatocyte (factor 2 - 2.5) is relatively low, when compared to the large range of the Chem-TEQ concentrations (factor 20) obtained when applying different modes of calculation. Conclusions and Outlook Overall, only a minor portion of the endocrine activity detected by bioassays could be linked to compounds identified by chemical analysis. In vitro assays for assessment of endocrine activities are useful as sensitive integrating methods that provide quantitative estimates of the total activity of particular receptor-mediated responses. Although discrepancies may also result from different bioanalytical approaches, it is overall likely that bioanalytical and not chemical analytical approaches give the correct estimate of endocrine disrupting potencies in environmental samples. As a conclusion, assessment of endocrine disruption based on chemical analysis alone does not appear sufficient and further research into the spectrum of substances with potential endocrine activity as well as into additive or even synergistic effects in complex environmental samples is urgently needed.     

Effects of bisphenol A on Gammarus fossarum and Lumbriculus variegatus in artificial indoor streams

The impact of bisphenol A (BPA) on Gammarus fossarum and Lumbriculus variegatus was studied in four artificial indoor streams (0, 5, 50 and 500?µg?L^?1 BPA, nominal) over 103 days in a pulse–dose exposure scenario (weekly BPA application). For G. fossarum populations at day 103, the proportions of juveniles and of breeding females from the highest BPA treatment were in tendency reduced. For individually exposed gammarid pairs an EC₁₀ of 17?µg?L^?1 BPA (nominal) for the proportion of reproductive females in the fourth brood was determined. During the first three broods, the largest brood size occurred at the highest BPA concentration, whereas in the fourth brood it decreased concentration-dependently (fourth brood EC₁₀?=?5?µg?L^?1 BPA, nominal). Effects on L. variegatus were a reduced population growth (103?d-EC₁₀ of 2?µg?L^?1 BPA, nominal) and an increase in dry weight and the number of segments in large, complete worms.     

Determination of 4-nonylphenol in carp blood samples by solid phase extraction and chromatographic techniques

In this study, selective methods were developed for isolation, purification, separation and determination of 4-nonylphenol (4NP) in biological samples. Several methods such as high-performance liquid chromatography (HPLC) with fluorescence and diode array detection and gas chromatography coupled to mass spectromotry (GC-MS) are described for the simultaneous determination of 4NP. The nonylphenols in the plasma of fish were extracted through solid phase process by using octadecyl, polymeric and octadecyl endcapping sorbents. The average recoveries in plasma samples spiked with 4NP of levels 1?µg?mL^?1 were between 80–95% using added surrogate standards. The aim of this study was to determine whether trace amounts of 4NP in fish plasma samples could be detected by solid phase extraction and chromatographic methods (HPLC, GC-MS). This technique of monitoring the levels of endocrine-disruptors in plasma samples is consistent, reliable as well as inexpensive.     

Determination of three endocrine disrupting chemicals,triclosan, 4-n-nonylphenol,and di-n-butyl phthalate using stir bar sorptive extraction in samples of different matrices

Three endocrine disrupting chemicals (EDCs), triclosan (TCS), 4-n-nonylphenol (4-n-NP), and di-n-butyl phthalate (DBP) were determined using stir bar sorptive extraction (SBSE) along with high-performance liquid chromatography/photodiode array detection (HPLC/DAD). Benzyl butyl phthalate was used as an internal standard. The targeted analytes could be rapidly determined with limits of quantification (LOQ) ranging from 4.1 (DBP), 10 (TCS), to 34 (4-n-NP)?µg?L^?1 in real samples such as bottled waters, personal care products, soaps, lotions, and urine. The results show that the developed analytical scheme is solvent-saving, efficient, and capable of fast screening samples for these common EDCs.     

腈菌唑不同对映体对丽斑麻蜥性腺系统的影响

腈菌唑(myclobutanil,MT)是一种应用广泛的手性杀菌剂,其手性对映体为(+)-腈菌唑(MT1)和(-)-腈菌唑(MT2)。腈菌唑手性单体具有不同的生物活性,但很少有其对爬行动物的对应选择毒性研究。为了评估腈菌唑手性单体对丽斑麻蜴性腺系统的毒性影响,将MT1(50 mg·kg-1)和MT2(50 mg·kg-1)以经口灌胃方式分别暴露给蜥蜴28 d。暴露期间,记录观察蜥蜴体重、血液中性激素(睾酮T和雌二醇E2)浓度以及性腺相关基因(3β-HSD、17β-HSD、CYP11A、CYP17、CYP19A、ER-α和AR)的表达图谱的变化。在MT1暴露组中,蜥蜴体重在28 d出现明显下降。而在MT2暴露组中,蜥蜴体重没有明显变化。雄性蜥蜴在经过1 d的暴露后,E2浓度在MT1暴露组中明显下降,而在MT2暴露组中明显上升。这些结果表明了腈菌唑手性单体的对映选择性毒性。在MT2暴露14 d后,雌性蜥蜴中CYP19A基因的表达上调弥补了体内E2浓度的降低。在MT1暴露的14 d,蜥蜴卵巢中观察到的CYP11A和CYP17基因表达下调以及CYP19A基因表达不变的这一现象解释了蜥蜴血液中E2和T的浓度减少。这些结果表明:MT1和MT2暴露对蜥蜴体内性激素造成不同的影响,而这些影响会相应改变性腺相关基因的表达。综上所述,MT1和MT2对性腺系统具有潜在的内分泌干扰效应,可能对蜥蜴造成不同程度的生殖损伤。     

邻苯二甲酸酯降解细菌的多样性、降解机理及环境应用

邻苯二甲酸酯(phthalic acid esters,PAEs)是一类对人体内分泌系统有干扰作用的持续性有机污染物(persistent organic pol utants,POPs)。PAEs在环境介质如水体、底泥和土壤中长期赋存会对生物体产生毒害效应,其分布广、浓度高和难降解等特点是限制有效环境治理的主要因素。作为环境的重要组成部分,微生物对污染物有很强的适应能力和高效的降解能力,这为PAEs的生物修复提供了可能。与物理化学修复法相比,微生物修复技术具有可控性强、修复面广和灵活性高等优势。本文综述了已报道的大部分PAEs降解细菌的种类及其代谢机制,并分析了其在PAEs污染水体和土壤修复中的应用现状与前景,以期为PAEs环境行为与生物修复研究提供参考。