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.

ABSORPTION SPECTRA OF 4f ELECTRON TRANSITIONS OF NEODYMIUM COMPLEX WITH 8-HYDROXYQUINOLINE AND OCTYLPHENOL POLY(ETHYLENEGLYCOL)ETHER

In this paper the absorption spectra of 4f electron transitions of the neodymlum complex with 8-hydroxyquinoline and octylphenol poly(ethyleneglycol)ether have been studied. The marked intensification of the band at low octylphenol poly(ethyleneglycol)ether concentration is found normally at 575 nm, and its resolution into three sharp bands centering at 572, 580 and 584 nm. The absorbances of the absorption maxima are 3.5 (at 572 nm), 7.2 (at 580 nm) and 10.2 (at 584 nm) times greater than that of the chloride.

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.

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.

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.

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.

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。

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。

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 .

高效液相色谱-串联质谱法测定环境水体中双酚A、辛基酚、壬基酚

建立了高效液相色谱-串联质谱测量水环境中的双酚A（BPA）、辛基酚（OP）、壬基酚（NP）的方法。提取方法基于液-液萃取，流动相为V（甲醇）-y（水）=90-10，流速200pL／min，运行时间为5rnin。质谱用来定量的碎片离子分别为：BPA，212．3；BPA-d16，223．4；OP，106．3；NP，106．3，定量采用内标法。仪器的检出限均为0．7pg，方法检出限均为0．07ng／L。对同一环境样品进行3个不同浓度（10、100、500ng／L）的加标来测得回收率：BPA 79．4％～84．3％，RSD 2．7％～3．4％；NP 78．9％～112．5％，RSD 1．9％～5．0％；OP 69．4％～122．7％，RSD 3．4％～11．3％。基于该方法，对大连旅顺地区主要河流和排污口水体中的BPA、NP和OP进行了检测，浓度范围为35．67-753．92ng／L，与国内其他调查区域比酚类物质污染处于中等水平，而低于国外类似调查区域。

高效液相色谱法测定饮料类食品中的类雌激素

利用OASIS HLB固相萃取柱富集和净化样品,采用高效液相色谱分离,紫外及荧光检测,建立了不同饮料基质中的壬基酚(NP)、辛基酚(OP)和双酚A(BPA)等类雌激素的测定方法,并用该方法对市售部分产品进行了测定.不同加标水平的BPA,NP和OP的回收率为91.08% ～103.19% ,其相对标准偏差为0.5% ～5.49% .该方法具有操作简单、灵敏度高和重现性好等优点.

冬季胶州湾及其周边河流中酚类环境激素的分布特征

分析青岛胶州湾及其临近河流中丁基酚、辛基酚、二氯酚和双酚A等环境激素的污染特征。结果表明，胶州湾水体中上述4种污染物的浓度分别为〈1．2-28．0，〈1．2～16．1，〈2．7-9．5和〈3．8～161．5ng／L；胶州湾沉积物中上述4种污染物的浓度分别为〈1．0～1．4，〈1．0-2．8，〈0．8～1．6和〈0．7～5．4ng／g。胶州湾内上述污染物均呈现东高西低的分布格局，说明湾内污染与沿岸工业分布和河流输入密切相关。胶州湾周围河流中上述污染物浓度远远高于湾内，其中墨水河污染最严重。文中同时讨论了酚类环境激素对当地生物的潜在危害。

液相色谱-串联质谱法同时测定纺织品和食品包装材料中的壬基酚、辛基酚和双酚A

建立了纺织品和食品包装材料中壬基酚、辛基酚和双酚A的液相色谱-串联质谱分析方法。不同类型的纺织品和食品包装材料样品采用加速溶剂萃取法,以无水乙醇为提取剂,在10.3 MPa和120℃下静态循环提取2次,提取液经Supelclean Envi-Carb石墨化碳黑固相萃取柱净化,收集甲醇-二氯甲烷(1∶4,V/V)洗脱液,采用Waters XBridge C18色谱柱,以甲醇-0.1%氨水溶液为流动相,梯度洗脱分离后,在LC/MS/MS多反应监测模式下进行定性与定量分析。壬基酚、辛基酚和双酚A的方法检出限为0.5μg/kg,在0.5～10μg/kg的3个添加水平范围内,纺织品样品的平均回收率为86.9%～92.5%,相对标准偏差均小于9.1%;食品包装材料样品的平均回收率为87.8%～93.0%,相对标准偏差均小于8.8%。本方法准确、快速、灵敏度高,可用于纺织品和食品包装材料的实际检验。

液相色谱串联质谱法测定化妆品中的双酚A、辛基酚及壬基酚

建立了护肤化妆品中双酚A、辛基酚和壬基酚的超高效液相色谱串联质谱分析方法。样品经二氯甲烷提取,氨基固相萃取柱净化后,用甲醇定容,采用Waters UPLC BEH C18色谱柱,以甲醇-0.05%氨水为流动相,梯度洗脱分离后,串联四极杆质谱多反应监测方式检测,以保留时间和子离子比定性,外标法定量。在优化条件下,该方法 5 min内可完成4种待测物的分析。双酚A、辛基酚和壬基酚在0.5～50.0μg/L范围内线性关系良好,相关系数均大于0.999,方法的定量下限(LOQs)均为0.5μg/kg;在加标水平为0.5、1.0、10.0μg/kg时,护肤霜和护肤水样品中4种待测物的平均加标回收率为80%～96%,相对标准偏差(n=6)小于15%。该方法准确、快速、灵敏,适用于护肤化妆品中双酚A、辛基酚和壬基酚的快速确认和定量检测。