A Study on Bisphenol A,Nonylphenol,and Octylphenol in Human Urine amples Detected by SPE-UPLC-MS

Objective To establish a comprehensive analytical method based on SPE‐UPLC‐MS for the simultaneous determination of bisphenol A （BPA）, nonylphenol （NP）, and octylphenol （OP） in urine samples. Methods Sixty urine samples collected from healthy subjects were analyzed for BPA, NP, and OP concentrations. The samples were de‐conjugated by adding β‐glucuronidase and sulfatase. After the enzymatic treatment, the samples were subjected to the OASIS HLB column solid phase extraction cartridges so as to be cleaned and concentrated. The UPLC separation was performed on a Acquity UPLCTM BEH C18 column （2.1×100 mm, 1.7 μm） with a gradient elution system of methanol‐water as the mobile phase. Triple‐quadrupole mass spectrometry analyzer was used for the qualitative and quantitative analysis of UPLC‐MS/MS system. Results The limit of detection of BPA, NP, and OP was 0.10, 0.10, and 0.15 ng/mL, respectively. The recoveries of BPA, NP and OP were 80.1%‐108%, 81.3%‐109%, and 81.5%‐98.7%, respectively. Among the 60 urine samples, BPA was detected in 8 samples at the level of 0.297‐32.7ng/mL, NP was detected in 29 samples at the level of 1.69‐27.8 ng/mL, and OP was detected in 17 samples at the level of 0.407‐11.1 ng/mL. Conclusion The method is simple with high sensitivity and selectivity, and is suitable for the determination of BPA, NP, and OP in urine. As shown by our analysis , BPA, NP, and OP appear to be prevalent in human urine. This is particularly true for NP. The results from our study is therefore valuable for future studies to assess the exposure to BPA, NP, and OP in the general population.

Distribution patterns of octylphenol and nonylphenol in the aquatic system at Mai Po Marshes Nature Reserve,a subtropical estuarine wetland in Hong Kong

Spatial and temporal distribution of octylphenol （OP） and nonylphenol （NP） in Mai Po Marshes, a subtropical estuarine wetland in Hong Kong, were investigated. Surface water samples were collected every month from 11 sites during the period of September- December 2004. Concentrations of OP and NP ranged from 11.3 to 348 ng/L and from 29 to 2591 ng/L, respectively. The high levels of NP and OP were found in November and December than in September and October. The levels of OP and NP have no significant spatial differences except September. Total organic matter in the sediments appeared to be an important factor in controlling the fate of these compounds in the aquatic environment.

Simultaneous determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in Guanting Reservoir using gas chromatography-mass spectrometry with selected ion monitoring

The wide occurrence of estrogenic compounds 4-tert-octylphenol, 4-nonylphenol, bisphenol A in surface water of Guanting Reservoir was successfully determined. The target compounds in water samples were preconcentrated by liquid-liquid extraction with dichloromethane, derivatized by trifluoroacetic anhydride, and quantified by gas chromatography-mass spectrometry(GC-MS) with selected ion monitoring(SIM). In the selected seven sampling sites(S1\_S7), the concentration of NP in sample S7 was significantly higher than the other in reservoir. The status of pollution in S3 and S7 were much more serious. The concentrations of OP, NP and BPA were in the range of 44.5—48.8, 221.6—349.6 and 30.2—82.7 ng/L, respectively. The pollutants were mainly inputted from the upper river and released from sediments in Guanting Reservoir.

Study of 4-t-octylphenol degradation and microbial community in granular sludge

In this study, the authors have investigated the effects of various factors on both aerobic and anaerobic degradation of 4-t-octylphenol （4-t-OP） in granular sludge. In comparison, the aerobic degradation rate was much higher than that of anaerobic degradation. The optimal pH values for 4-t-OP degradation in granular sludge were 9 and 7 under aerobic and anaerobic conditions, respectively. And the degradation rate decreased with an increase in the initial 4-t-OP concentration. Addition of yeast extract or homologous compounds such as phenol also enhanced the 4-t-OP degradation, especially under the aerobic condition. To investigate the bacterial community in this study, the denaturing gradient gel electrophoresis （DGGE） method was applied, based on the primers, for the 16S rDNA V3 region of bacteria, γ-proteobacteria and bacillus were identified as the major species of sludge.

Effect of maternal exposure to octylphenol (4-tert-octylphenol) on the growth of the adrenal gland in male albino rats

4-tert-octylphenol (OP) is environmental pollutants that have been shown widespread impact estrogenic and toxic to the cells of mammals in culture. The effects of OP on the reproductive system of adult male vertebrates especially humans are virtually unknown. Thus, in the present investigation, pregnant females of albino rats were orally treated during pregnancy and until 21 days after birth (the period of lactation) with octylphenol (OP) at doses 0 (vehicle: corn oil), 40 mg/kg and 120 mg/kg on the epididymis of male rats at puberty (12 weeks of age). The present result showed that there is non-significant in the number;the size of newborn rats and there increased in mortality rate of newborn rats of the pregnant female treatment with dose low-and high-octylphenol compared to the control group. there is increased in the average body weight and percentage of gain in body weight of male rats from mothers of small treatment (G2, G3) and the control group (G1) for 12 weeks of age. Also, histological results showed that the adrenal gland in the group which was given high dose of octylphenol (G3) show that Severe histological changes in the cortex. When examining medulla and found large areas of necrosis and cell degradation, necrosis and cell death sharply.

Fe/C Modified TiO_2 Photocatalyst and Photodegradation of 4-t-octylphenol

[Objective]The research aimed to study synthesis of the TiO2 photocatalyst modified by Fe/C and photodegradation of 4-t-octylphenol.[Method]Fe/C modified TiO2 photocatalyst was made by sol-gel and solvothermal synthesis methods.4-t-octylphenol as test object,photocatalytic performance of the catalyst was investigated.Influences of the Fe doping amount,catalyst amount,pH and sun-light irradiation on reaction were discussed.Moreover,catalyst performance under the condition of interfering ion existence was studied.[Result]When Fe/C doping amount was 0.6%,under the reaction condition of 25 ℃,pH =9.0,300 W mercury lamp and 1.0 g/L of catalyst amount,4-t-octylphenol concentration decreased from 1.00 to 0.02 mg/L by degradation for 100 min.Rises of pH and light intensity could improve catalyst efficiency.The existences of Na ＋,K ＋ and Ca2＋ had no effect on degradation activity of the catalyst.[Conclusion]Fe/C modified TiO2 photocatalyst had better degradation effect on environmental hormone in the sewage.

Radiolytic degradation and mechanism study of electron beam-irradiated solutions of 4-tert-octylphenol

In this study, we have investigated the degradation and primary radiolytic degradation mechanism of 4-tert-octylphenol (4-t-OP) by using of electron beam (EB) -irradiation. The results show that at an absorbed dose of 10 kGy and an initial concentration of 25 mg·L -1 , the degradation of 4-t-OP in a methanol/water reduction system is higher than in a acetonitrile/water oxidation system by 19.4% and higher than in an acetone/water system by 26.8%, which is due to both of ·OH and e aq - playing an important role in the decomposition of 4-t-OP, although the latter is more effective. The degradation rate of 4-t-OP will decrease with increment of absorbed dose in a methanol/water solution, and increase with decrement of initial concentration at a constant absorbed dose. The degradation efficiency will also decrease with the addition of anions and H 2 O 2 into the solution. A system saturated with N 2 will make an increment in the degradation of 4-t-OP. The pH value of solution has been also found to affect the degradation efficiency, while the degradation is more efficient in alkaline conditions. Finally, the initial products involved in degradation reaction have been determined to be ethylbenzene, styrene, bicyclo[4.2.0]octa-1,3,5-triene, 2,2,4-trimethylpentane and p-tert-butyl-phenol, which may arise from e aq - attack at the position of the alkyl side chain of 4-t-OP molecule. The results have been revealed that EB irradiation is a promising method for degradation of 4-t-OP, and e aq - may be main reactive species to attack at the position of the alkyl side chain of 4-t-OP.

药用橡胶塞中可提取硫和4-叔辛基苯酚及2-巯基苯并噻唑的检测

目的建立高效液相色谱法同时测定药用卤化丁基橡胶塞中可提取硫、4-叔辛基苯酚及2-巯基苯并噻唑的含量。方法使用甲苯-甲醇混合溶液作为提取溶剂,采用ZORBAX SB-C_(18)(150 mm×4.6 mm,5μm)色谱柱,流动相为乙腈-水(85:15),流速1.0 mL·min^(-1),检测波长280 nm,柱温为40℃,进样量20μL。结果可提取硫、4-叔辛基苯酚和2-巯基苯并噻唑的检测质量浓度线性范围分别为0.20~501.00μg·mL^(-1)(r=0.9998)、0.20~502.95μg·mL^(-1)(r=0.9999)、0.22~547.53μg·mL^(-1)(r=0.9998),检出限分别为0.40、0.25和0.15μg·mL^(-1);精密度、稳定性的相对标准偏差(RSD)均<3%;提取回收率分别为93.5%~104.8%、99.0%~100.6%和103.0%~107.7%;迁移回收率分别为97.0%~101.8%、98.7%~110.3%和89.3%~94.0%。结论该方法灵敏快速、操作简便、重复性好,可用于药用卤化丁基橡胶塞中可提取硫、4-叔辛基苯酚及2-巯基苯并噻唑含量的测定。

Spatial–temporal distribution and potential ecological risk assessment of nonylphenol and octylphenol in riverine outlets of Pearl River Delta, China

The aquatic environments of the Pearl River Delta in Southern China are subjected to contamination with various industrial chemicals from local industries. In this paper, the occurrence, seasonal variation and spatial distribution of alkylphenol octylphenol （OP） and nonylphenol （NP） in fiver surface water and sediments in the runoff outlets of the Pearl River Delta were investigated. NP and OP were detected in all water and sediment samples and their mean concentrations in surface water during the dry season ranged from 810 to 3366 ng/L and 85.5 to 581 ng/L, respectively, and those in sediments ranged from 14.2 to 95.2 ng/g dw and 0.4 to 3.0 ng/g dw, respectively. In surface water, much higher concentrations were detected in the dry season than those in the wet season. In sediments, the concentrations in the dry season were also mostly higher. High concentrations of NP and OP were found in Humen outlet, likely due to high levels of domestic and industrial wastewater discharges. An ecological risk assessment with the use of hazard quotient （HQ） was also carried out and the HQvalues ranged from 3.6 × 10^-5 to 35 and 64% of samples gave a HQ 〉 1, indicating that the current levels of NP and OP pose a significant risk to the relevant aquatic organisms in the region.

Determination of 4-tert-octylphenol in surface water samples of Jinan in China by solid phase extraction coupled with GC-MS

Octylphenols, considered as xenoestrogens, mainly exist as 4-tert-octylphenol （OP） in aquatic environments. The high stability and accumulation of OP in aquatic systems have caused endocrine disruption. The OP in surface water in Jinan, China was analyzed by gas chromatography-mass spectrometry （GC-MS） coupled with solid phase extraction （SPE）. Water samples were extracted by SPE on a cartridge system containing C-18 as sorbent. To increase sensitivity and selectivity, OP was derivatized to 4-tert-octyl-phenoxy silane. With the use of phenanthrene-d10 as internal standard, the detection limit based on signal-to-noise ratio （S/N = 3） was 0.06 ng/mL. The average recovery was from 84.67% to 109.7%. The precision of the method given as the relative standard deviations （RSD） was within the range 6.24%-12.96%. In the target water samples, the concentrations of OP were as follows： 15.88-71.24 ng/L for Jinxiuchuan Reservoir, 3.850-26.68 ng/L for the city moat, 6.930-41.56 ng/L for Daming Lake, 66.03-474.2 ng/L for Xiaoqing River, 14.66-17.72 ng/L for the Yellow River, and 10.60-26.43 ng/L for Queshan Reservoir. The Xiaoqing River was seriously polluted due to the discharge of wastewater from Jinan. Jinxiuchuan Reservoir had a higher concentration of OP compared with the Yellow River and Queshan Reservoir, which is ascribed to the surrounding human activities. These data are reported for the first time, providing strong support for the control of OP pollution in Jinan.

A simple and sensitive method for the determination of 4-n-octylphenol based on multi-walled carbon nanotubes modified glassy carbon electrode

A simple and sensitive electroanalytical method was presented for the determination of 4-n-octylphenol （OP） based on multi-walled carbon nanotubes （MWCNTs） modified glassy carbon electrode （GCE）. OP was directly oxidized on the MWCNTs/GCE, and the electrochemical oxidation mechanism was demonstrated by a one-electron and one-proton process in the reaction. The oxidation peak current of OP was significantly enhanced by the use of MWCNTs/GCE compared with those of bare glassy carbon electrode, suggesting that the modified electrode can remarkably improve the performance for OP determination. Factors influencing the detection processes were optimized. Under these optimal conditions, a linear relationship between concentration of OP and current response was obtained in the range of 5 × 10-8 to 1× 10-5 mol/L with a detection limit of 1.5 × 10-8 mol/L and correlation coefficient 0.9986. The modified electrode showed good selectivity, sensitivity, reproducibility and high stability.

辛基酚聚氧乙烯醚协同煤油改善高灰细煤浮选试验研究

针对传统捕收剂对高灰细煤浮选产率低、选择性差等问题,采用了辛基酚聚氧乙烯醚(OP-4)与煤油协同浮选某地高灰无烟煤,探究了OP-4的用量和复合方式对高灰细煤浮选的影响。结果表明:OP-4与煤油分步投加时的浮选效果优于同时投加;相比于纯煤油,60 g/t的OP-4与1200 g/t的煤油分步投加,浮选的可燃体回收率提高了8.29%,浮选完善度提高了15.55%。当OP-4用量为120 g/t时,浮选完善度反而下降。

气相色谱-质谱联用同时测定饮用水中辛基酚和壬基酚

气相色谱-质谱联用,同时测定饮用水中辛基酚和壬基酚。以甲苯为萃取溶剂液液萃取,浓缩定容后,内标法定量。辛基酚和壬基酚在0.01~2.00mg/L浓度范围内线性关系良好,其相关系数(r2)都大于0.995。二者方法检出限分别为0.007μg/L和0.033μg/L,回收率(3个加标水平条件下)为83.9%~104.9%,相对标准偏差(RSD,n=6)为2.0%~8.4%。该方法能够简单准确地同时测定饮用水中的辛基酚和壬基酚。

HP-β-CD降低表面活性剂复配体系中TO-5对OP-20的紫外光谱的干扰及其机理分析

采用辛基酚聚氧乙烯醚(OP-20)与异构十三醇聚氧乙烯醚(TO-5)复配体系中,由于TO-5的存在会对OP-20的吸光度及临界胶束浓度(CMC)产生明显影响,造成检测结果不准确。为此以羟丙基-β-环糊精(HP-β-CD)为掩蔽剂,来消除TO-5产生的干扰。虽然TO-5在250~350 nm范围内无明显吸收峰,但是TO-5能增强OP-20在275 nm处的吸光度,并且还可以显著降低OP-20的表观CMC。当水溶液中TO-5的浓度分别为0.20 mmol/L和0.30 mmol/L时,OP-20的表观CMC由0.279 mmol/L分别降低至0.265 mmol/L和0.234 mmol/L。研究结果表明,加入HP-β-CD后,0.20 mmol/L OP-20及其在0.20 mmol/L TO-5溶液中的吸光度分别为0.264和0.262,变化幅度仅为0.76%。研究结果还表明,HP-β-CD具有阻碍OP-20形成胶束的作用,Job's实验表明HP-β-CD与OP-20按摩尔比1∶1进行包结,加入HP-β-CD后,紫外光谱法能够准确检测OP-20/TO-5复配体系中OP-20的含量,回收率为99.17%~99.97%,TO-5的干扰显著减小。FT-IR和1H-NMR的实验结果表明,OP-20进入HP-β-CD分子内腔之中形成包结物,是HP-β-CD消除TO-5对OP-20的紫外光谱干扰和阻止OP-20形成胶束的根本原因。

壬基酚与辛基酚单独及联合暴露对大鼠肠道损伤的影响

两种典型环境内分泌干扰物——壬基酚(Nonylphenol,NP)与辛基酚(Octylphenol,OP),常常同时存在于自然环境中,经口摄入为它们进入人体内的主要途径。因此,NP与OP可能会对消化系统产生影响。目的:研究NP与OP单独及联合暴露对大鼠肠道损伤的影响。方法:将不同浓度的NP与OP单独或联合灌胃大鼠28天后,观察各组大鼠肠道氧化应激、通透性、炎症及肠道细胞凋亡情况。结果发现:NP与OP单独或联合暴露均会导致结肠组织结构破坏,紧密连接Claudin-1和Occludin蛋白表达水平下降,抗氧化酶活性发生改变,细胞因子IL-1β、TNF-α与IFN-γ表达水平上升,凋亡相关蛋白Caspase-3、Casspase-12、Bax和Bcl-2表达水平增加。结论:NP与OP单独或联合暴露均可通过改变肠道通透性、诱导大鼠肠道促炎细胞因子产生、降低抗氧化酶表达并诱导肠道细胞凋亡而对大鼠肠道造成不同程度的损伤。本研究对于全面评估环境内分泌干扰物联合暴露的健康风险,探索有效的预防干预措施,以及修订完善相关的卫生标准限值,具有重要意义。

复合药剂对独居石与萤石浮选分离效果的影响及作用机理

通过单矿物浮选与人工混合矿浮选、Zeta电位分析、接触角及XPS测试,研究复合捕收剂(辛基羟肟酸(OHA)+辛基酚聚氧乙烯醚(OP10))和抑制剂(乙二胺四乙酸(EDTA))对独居石与萤石浮选分离效果的影响及作用机理。结果表明:OP10能够显著提高OHA对独居石的捕收能力。相对于仅使用单一捕收剂OHA,使用复合捕收剂OHA/OP10对独居石的浮选回收率可提高13.91%;EDTA对萤石选择性抑制效果优于水玻璃;复合捕收剂OHA/OP10与抑制剂EDTA联合使用对独居石和萤石的浮选分离效果优于使用OHA和水玻璃联合使用时的分离效果。OP10和OHA能够协同吸附在独居石表面,强化其表面疏水性,提高其可浮性;EDTA能够抑制复合捕收剂OHA/OP10在萤石表面的吸附,而对独居石的影响较弱,从而提高独居石与萤石的浮选分离效率。

表面增强拉曼散射与分子印迹技术快速检测痕量辛基酚的试验研究

辛基酚广泛应用于涂装、橡胶等多种行业,是典型的酚类内分泌干扰物(Phenolic Endocrine Disrupting,PEDs)。环境介质中低浓度的辛基酚也可能造成很大的环境危害,亟待开发高效、快速的检测方法,预警和预报其环境风险。本文通过制备以银粒子为核,表面分子印迹聚合物为壳的银核辛基酚印迹微球,试验表面增强拉曼散射与分子印迹技术联用快速检测痕量辛基酚的方法。透射电镜(TEM)、X-衍射(XRD)和元素能谱分析(Energy Dispersive Spectroscopy,EDS)表征的结果表明:银核辛基酚印迹微球是银核外包裹二氧化硅的核壳结构,辛基酚印迹在壳层的表面,壳层不影响银核的晶型结构。壳层厚度影响银核辛基酚印迹微球选择性吸附辛基酚及银核表面拉曼光增强效果,最佳壳层厚度为25 nm。表面增强拉曼光谱与分子印迹技术联用检测辛基酚的最低检测限为10~(-12)mol/L。

HPLC-ELSD法测定纺织品中辛基酚聚氧乙烯醚

以甲醇为提取剂,在60℃下振荡萃取纺织品,以甲醇-水-乙腈(80:15:5,体积比)为流动相,采用蒸发光散射检测-高效液相色谱法(HPLC-ELSD)测定了纺织品中辛基酚聚氧乙烯醚(OPEO)的残留量。该方法不受OPEO未知聚合度的影响,操作简单快捷、定量可靠、重复性好,加标回收率在89.80%~104.26%范围,相对标准偏差为1.60%~6.06%。

多壁碳纳米管修饰可抛式电极的构建及对环境水样中辛基酚的检测

采用柔性涤纶树脂(PET)片为电极基底,使用物理气相沉淀和纳米材料修饰技术,将金纳米粒子和多壁碳纳米管(MWCNTs)修饰到电极表面,制备了一种简便、高效的可抛式电化学传感器,可用于环境水样中辛基酚的检测。通过扫描电镜(SEM)和原子力显微镜(AFM)研究了电极的表面形貌,通过循环伏安和线性扫描伏安研究了修饰电极的电化学行为。优化了金膜溅射时间、碳纳米管修饰量及电解液pH等条件。辛基酚的线性范围为0.05~5 mg·L^(-1),检出限为0.02 mg·L^(-1),通过标准添加回收实验,应用于环境水样中辛基酚的测定,回收率在86.0%~109.6%之间,相对标准偏差(RSD)小于12.3%。

洪季珠江三角洲水系烷基酚污染状况研究

对夏季珠江三角洲河流及珠江口表层水中溶解态的壬基酚 (NPs)和辛基酚 (OP)的污染状况进行了分析 .结果表明 ,河流样品中除珠江正干平洲水道口、沙湾水道口及西江虎跳门处NPs值较高分别达 98 84、12 9 82和 16 4 98ng/L外 ,其他地点均为 <2 0～ 4 0ng/L ;伶仃洋及近海表层水NPs含量较低为 <10～ 14ng/L .OP值以澳门内港处最高为 8 5 4ng/L ,另外在白鹅潭、沙湾水道口和虎跳门处分别为 2 89、2 4 4、2 12ng/L ,其余采样点均低于检测限 2ng/L ,伶仃洋及近海表层水样OP值低于检测限 1ng/L .