Simultaneous Determination of Bisphenols and Alkylphenols in Water by Solid Phase Extraction and Ultra Performance Liquid Chromatography-tandem Mass Spectrometry

To establish an analytical method for determination of four bisphenols （BPA, BPB, BPF, and BPS） and two alkylphenols （4-n-OP, 4-n-NP） in water by ultra performance liquid chromatography- tandem mass spectrometry （UPLC/MS/MS）. The water samples were extracted and condensed with solid-phase extraction （SPE） using C18 cartridges and eluted by acetonitrile. Separation was carried out with Acquity BEH C8 column and detection were performed by UPLC/MS/MS. Quantification was calculated by using the internal standard BPA-d16 and 4-n-NP-d8. The linear correlation coefficients of these compounds in the range of 1.0-100.0μg/L were all over 0.999. The minimum detectable concentrations were 0.75-1.0 ng/L, and the recoveries ranged from 87.0% to 106.9%.

Comparative Interactions of Anesthetic Alkylphenols with Lipid Membranes

Objective: While substituted phenols have a variety of pharmacological activity, the mechanism underlying their anesthetic effects remains uncertain especially about the critical target. We characterized the lipid membrane-interacting properties of different phenols by comparing with general anesthetic propofol and local anesthetics. Based on the results, we also studied the pharmacological effects possibly associated with their membrane interactivities. Methods: 1,6-Diphenyl-1,3,5-hexatriene-labeled lipid bilayer membranes were prepared with 1,2-dipalmitoyl-phosphatidylcholine as model membranes and with different phospholipids and cholesterol to mimic neuronal membranes. These membrane preparations were treated with phenols and anesthetics at 1 - 200 μM, followed by measuring the fluorescence polarization to determine the membrane interactivities to change membrane fluidity. Antioxidant effects were fluorometrically determined using diphenyl-1-pyrenylphosphine-incorporated liposomes which were treated with 10 - 100 μM phenols, and then peroxidized with 10 μM peroxynitrite. Results: Several phenols interacted with the model membranes and the neuronal mimetic membranes to increase their fluidity at 1 - 10 μM as well as lidocaine and bupivacaine did at 50 - 200 μM. Their comparative potencies were propofol > thymol > isothymol > guaiacol > phenol > eugenol, and bupivacaine > lidocaine, consistent with the rank order of neuro-activity. These phenols inhibited membrane lipid peroxidation at 10 and 100 μM with the potencies correlating to their membrane interactivities. Conclusion: The structure-specific membrane interaction is at least in part responsible for the pharmacology of anesthetic alkylphenols. Membrane-interacting antioxidant alkylphenols may be protective against the peroxynitrite-relating ischemia/reperfusion injury.

A Simplified Analytical Procedure for Simultaneous Determination of Alkylphenol Ethoxylates and Brominated Flame Retardants in Fish Tissue Samples from Vaal River,South Africa

In this study, the concentration of alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) were determined in fish samples, Labeo umbratus and Carp, collected from the Vaal River in South Africa. Ultrasonic-assisted extraction technique was used to extract the organic contaminants from fish samples, and the resulting extract was purified by sulphuric acid lipid removal followed by Strata X-cartridge SPE clean-up. The APEs and BFRs were derivatized using heptafluorobutyric anhydride before analysis with GC-MS. In both types of fish samples, lower oligomers of APEs were more abundant than the higher oligomers, while HBCD, BDE99 and PBB101 were the dominant BFRs. The concentrations of these pollutants ranged from 1.061 ng/g lipids (t-BP) in Labeo umbratus to 11.860 ng/g lipids (HBCD) in Carp.

Alkylphenols and alkylphenol ethoxylates in dust from homes, offices and computer laboratories: Implication for personal exposure via inadvertent dust ingestion

In the present study,the levels of alkylphenols(APs)and alkylphenol ethoxylates(APEs)in indoor dust of three different microenvironments were measured and daily intake via dust ingestion estimated.Alkylphenols and alkylphenol ethoxylates were extracted with the aid of sonication and analyzed by gas chromatography mass spectrometry after heptafluorobutyric anhydride derivatization.The concentration values of these pollutants ranged from 1918e10935 ng g
1;343e12438 ng g
1 and 1122 e15324 ng g
1 in dust samples from homes,computer laboratories and offices,respectively.In all the microenvironment studied,di-NPE and mono-NPE were the most abundant isomers suggesting widespread use of NPE-based consumer products in the studied microenvironments.The daily exposure dose(DED)was estimated using min,mean and max concentrations of APs and APEs detected in respected microenvironments.The worst case scenario for the exposure of APEs was highest for toddlers at 146 ng kg
1 bw day
1 followed by teenagers at 11.3 ng kg
1 bw day
1 and adults at daily exposure of 8.53 ng kg
1 bw day
1.Though the daily exposure doses are low,there is a cause for concern as these surfactants are not regulated in many developing countries and their use may be increasing.

酚类环境内分泌干扰物微生物降解研究进展

环境内分泌干扰物(EDCs)又名环境激素,具有类似激素的结构和效应,能够干扰生物体的内分泌系统,危害人类和动物健康。聚焦典型酚类EDCs,包括烷基酚(APs)、双酚类(BPs)和氯酚(CPs)的微生物降解研究。受污染的土壤、河流、沉积物或活性污泥中存在并可分离出能够有效降解酚类EDCs的细菌和真菌,这些降解菌在污染土壤或水体的生物原位修复,去除废水中酚类EDCs等方面具有良好的应用前景。系统综述了好氧和厌氧条件下酚类EDCs的降解功能菌及其降解途径,总结了酚类EDCs的降解功能酶和功能基因,包括参与羟化作用的单加氧酶和羟化酶、参与环裂解的双加氧酶和还原脱氯过程需要的还原脱卤酶等,旨在为推动高效削减酚类EDCs的微生物法技术创新提供科学依据。

Occurrence and fate of endogenous steroid hormones,alkylphenol ethoxylates, bisphenol A and phthalates in municipal sewage treatment systems

Steroid hormones, alkylphenol ethoxylates（APEOs） and phthalic acid esters（PAEs） are emerging endocrine disrupting chemicals（EDCs） that can interfere with the endocrine function in organisms at low concentrations. The occurrence, distribution behavior, removal rate and the fate of 31 target EDCs in sewage treatment plants, which consist of various treatment facilities and receiving water in Hong Kong, were investigated. Estrone,nonylphenol-di-ethoxylate and diethyl phthalate were found to be dominant in each group of influent samples with concentrations ranging from 11–33, 747–3945 and 445–4635 ng/L,respectively. Conversely, progesterone, nonylphenol-mono-ethoxylate and bis（2-ethylhexyl）phthalate were the most abundant in dewatered sludge, with concentrations ranging from 0.9–237, 75–19,743 and 4310–37,016 ng/g（dry weight）. The removal rates of primary sedimentation and disinfection approaches were lower than 30% for most of the chemicals,while those of activated sludge and reverse osmosis were greater than 80% for more than two-thirds of the compounds, noticeably decreasing the estrogenic risk of sewage discharged into the environment. Steroid hormones were removed via biological degradation, while some APEOs and PAEs adsorbed to the sludge. Victoria Harbor poses a low to medium estrogenic risk mainly contributed by estrone and estradiol and deserves attention.

气相色谱-质谱法测定沉积物中的烷基酚和双酚A

本文以内分泌干扰物烷基酚和双酚A为研究对象,使用加速溶剂萃取-硅胶柱净化-气相色谱质谱联用仪,建立了同时测定沉积物中8种痕量APs和BPA的检测方法.沉积物样品经冷冻干燥后,用丙酮-二氯甲烷(V/V=1/2)为萃取溶剂,在100℃下进行加速溶剂萃取.萃取液浓缩后使用硅胶柱净化,经气相色谱分离、质谱检测,根据保留时间、质谱碎片及其丰度定性,内标法定量.结果显示,待测物在10—2000μg·L^(-1)范围内线性关系良好,相关系数大于0.9994,检出限在0.6—1.9μg·kg^(-1)之间.目标物在200、500μg·L^(-1)标准溶液中相对标准偏差(n=7)为1.9%—5.4%,加标样品回收率为85.7%—99.5%.用本方法检测天津某河流的沉积物样品,4-丁基苯酚、4-叔辛基苯酚、4-壬基酚、双酚A被检出,实际样品中APs和BPA的加标回收率为84.5%—97.4%.实验表明,使用该方法检测沉积物中的APs和BPA,操作简便,灵敏度高,准确性和重现性良好,可满足沉积物中痕量APs和BPA的检测需要.

服饰中烷基酚聚氧乙烯醚测定方法探讨

烷基酚聚氧乙烯醚(APEOs)作为表面活性剂在服装生产、加工过程中应用广泛,一旦残留将对环境产生严重的危害,必须对其加强监管和检测。目前国内已经制定和实施了服装产品中烷基酚聚氧乙烯醚检测方法标准,但在实际检验过程中存在同一样品尤其羽绒产品,结果差异较大,实验结果经常无法统计,实验室间试验结果无可比性等问题。针对上述问题,本文结合日常大量检验测试探讨影响服装产品APEO准确测定的影响因素,统一实验操作,确保实验室的检测数据的准确性和重现性,提高检测能力。

Catalytic fast pyrolysis of walnut shell for alkylphenols production with nitrogen-doped activated carbon catalyst

Alkylphenols are a group of valuable phenolic compounds that can be derived from lignocellulosic biomass.In this study,three activated carbons(ACs)were prepared for catalytic fast pyrolysis(CFP)of walnut shell to produce alkylphenols,including nitrogen-doped walnut shell-derived activated carbon(N/WSAC),nitrogen-doped rice husk-derived activated carbon(N/RHAC)and walnut shell-derived activated carbon(WSAC).Pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS)experiments were carried out to reveal the influences of AC type,pyrolytic temperature,and AC-to-walnut shell(AC-to-WS)ratio on the product distributions.Results showed that with nitrogen doping,the N/WSAC possessed stronger capability than WSAC toward the alkylphenols production,and moreover,the N/WSAC also exhibited better effects than N/RHAC to prepare alkylphenols.Under the catalysis of N/WSAC,yields of alkylphenols were significantly increased,especially phenol,cresol and 4-ethylphenol.As the increase of pyrolytic temperature,the alkylphenols yield first increased and then decreased,while high selectivity could be obtained at low pyrolytic temperatures.Such a trend was also observed as the AC-to-WS ratio continuously increased.The alkylphenols production achieved a maximal yield of 44.19 mg/g with the corresponding selectivity of 34.7%at the pyrolytic temperature of 400℃and AC-to-WS ratio of 3,compared with those of only 4.67 mg/g and 6.1%without catalyst.In addition,the possible formation mechanism of alkylphenols was also proposed with the catalysis of N/WSAC.

烷基酚聚氧乙烯醚对混凝土中钢筋氯盐耐蚀性的影响

为研究不同浓度的烷基酚聚氧乙烯醚(APEO)缓蚀阻锈效果,开展钢筋电化学试验,研究不同APEO浓度对钢筋电化学行为和缓蚀效果的影响。结果表明,随着APEO浓度的增加,钢筋的电化学行为出现三阶段变化特征,即激发—抑制—再激发;当APEO浓度达30mg/L时,腐蚀溶液中钢筋表面阻抗最大,腐蚀电流最小,电化学反应强度最弱;当APEO浓度过低时,在钢筋表面难以形成包裹完整的钝化膜;当APEO浓度过高时,作为金属络合物的APEO易与钢筋表面Fe发生络合反应,加剧钢筋腐蚀反应。因此,掺入一定浓度的APEO,可有效提高钢筋抗腐蚀性,延长钢筋混凝土结构在Cl^(-)腐蚀环境下的服役寿命。

固相萃取-高效液相色谱-荧光检测法快速测定水中9种烷基酚和双酚A

建立了一种基于固相萃取-高效液相色谱-荧光检测技术快速测定实际水样中9种痕量烷基酚类化合物和双酚A的方法。首先筛选出能高分离度分离10种目标物的色谱柱,并进一步优化了柱温、检测波长、流动相流速和梯度时间等色谱条件。实现了10.0 min内快速分离检测10种目标物,显著提高了色谱分析流程的分离效果和检测效率。10种目标物在0.08(0.16)~10.00μg/L浓度范围内工作曲线线性关系良好,相关系数均大于0.998。方法检出限为0.02~0.04μg/L,定量限为0.08~0.16μg/L。地下水、地表水和工业废水的加标回收率分别为81.4%~98.0%、88.9%~103.0%和77.3%~107.8%,相对标准偏差为1.5%~7.3%、1.8%~5.6%和3.0%~7.4%。方法分析速度快、灵敏度好、重现性好、准确度高,能够用于实际水样中烷基酚类化合物和双酚A的测定。

烷基苯酚二硫化物CV-50在EPDM配方中的性能研究

对比研究了新型硫黄给予体烷基苯酚二硫化物CV-50与DTDM-80、CLD-80等硫黄给予体硫化剂在EPDM配方中的应用特性。结果表明:CV-50在高温硫化时不会生成致癌性的亚硝胺及亚硝胺类物质,相较于常用的硫载体硫化剂,其气味最轻;CV-50所对应胶料的力学性能、耐热氧老化性能、压缩永久变形等基本与之相当,但其环保且价格优惠,因而烷基苯酚二硫化物CV-50是DTDM-80、CLD-80等的理想环保替代物。

Controls on alkylphenol occurrence and distribution in oils from lacustrine rift basins in East China

Oils from two lacustrine rift basins in east China are thoroughly investigated using geochemical method to understand controls on alkylphenol occurrence and distribution in oils. Oils in the Lujiapu Depression, Kailu Basin are derived from the Cretaceous source rocks, and those in the Dongying De- pression, Bohai Bay Basin, from the Tertiary source rocks. All oils are experienced relatively short distance of migration and have similar maturity in each basin. Differences in homologue distributions from different oilfields are most likely caused by organic facies variation of source rocks. The oils in the Lujiapu Depression are characterized by high proportion of C3 alkylphenols (prefixes refer to the number of alkylcarbons joined to the aromatic ring of the phenol molecule) and low proportion of cre- sols and C2 alkylphenols compared to oils from the Dongying Depression. Alkylphenol isomer distri- bution is possibly affected by depositional environment especially for C3 alkylphenols. Dysoxic fresh- water environment is favorable for the formation of propyl or isopropyl substituted C3 alkylphenols, while highly reducing saline water is more suitable for trimethyl substituted C3 alkylphenols. Variations in alkylphenol concentrations within a petroleum system are controlled mainly by secondary migration processes with alkylphenol concentrations decreasing along migration direction. Interestingly, coupled with geological factors, a subtle change of alkylphenol concentrations can be applied to differentiate carrier systems. When oil migrates through sandy beds, concentrations of total alkylphenols decrease dramatically with migration distance, while such change is less significant when oil migrates vertically along faults. However, most isomer ratios potentially related to migration distance are not as effective as those alkylcarbazoles in migration diagnosis due to complicated affecting factors.

液相色谱串联质谱法测定纺织品和涂料中的烷基酚聚氧乙烯醚

验证了用液相色谱串联质谱法测定纺织品和涂料中的烷基酚聚氧乙烯醚的方法的实用性,及测试中需特别注意的方面,并给出了此方法的精密性和准确度。对色谱条件进行了进一步优化,给出了详尽的液相色谱串联质谱法测定烷基酚聚氧乙烯醚的参数。

水基胶中多种化合物的同时测定

建立了同时测定水基胶中异噻唑啉酮类杀菌剂和双酚A、壬基酚、辛基酚和邻苯二甲酸酯类环境激素的方法。样品经甲醇提取后,直接进超高效液相色谱-串联质谱(UPLC-MS/MS)分析,采用同位素内标法定量。研究结果表明:所有化合物在20~500 ng/mL浓度范围内线性关系良好(R^(2)≥0.9983),检出限(LOD)和定量限(LOQ)分别在0.009~0.115 mg/kg和0.029~0.382 mg/kg范围内;不同浓度水平下,所有待测物的回收率在84.1%~105.6%之间,日间相对标准偏差(RSD)小于8.0%;对60个实际样品进行检测,所有样品均检出异噻唑啉酮类杀菌剂,各有1个样品检出壬基酚和邻苯二甲酸二丁酯。本方法检测效率高,节约检测成本,尤其适合实验室大批量样品的日常检测。

固相萃取-衍生化-气相色谱质谱法测定水中9种烷基酚类化合物

针对地表水、地下水及饮用水中9种烷基酚类化合物的含量检测,建立了一种适合于气相色谱-质谱分析的衍生化方法。分别对样品预处理的衍生化温度、反应时间、水体样品pH、洗脱溶剂类型及用量进行优化。优化结果表明,烷基酚类化合物的质量浓度在20.0~1000μg/L范围内与色谱峰面积具有良好的线性关系,线性相关系数均不低于0.9991,方法检出限为4.49~9.46 ng/L。地表水、地下水及饮用水样品加标回收率为77.6%~98.8%,测定结果的相对标准偏差不大于11.4%(n=7)。该方法适用于地表水、地下水及饮用水中烷基酚类化合物的检测。

纺织品中酚类化合物的法规标准及分析技术研究进展

纺织品在生产加工过程中会使用或接触到各种染化料助剂,并有可能残留在最终产品中,造成潜在的环境与健康危害;同时,纺织品服装的安全环保性越来越受到重视,绿色、生态纺织品的概念逐渐深入人心。为此,以酚类化合物这一大类典型环境污染物为研究对象,概述了目前国内外纺织品法规/标准的限制和要求情况,特别讨论了法规标准中烷基酚的复杂信息。同时,从样品前处理及分析测试方法2个方面,综述了纺织品中含氯苯酚、烷基酚、双酚类等酚类化合物的检测技术和检测标准进展。最后,对该领域存在的问题和研究趋势进行了初步的小结和展望,指出开发多类别残留物筛查检测技术、实施纺织品全链条化学污染物高效识别、开展与消费者安全直接相关的暴露风险评价等未来发展方向,旨在为纺织品化学安全检测和质量控制提供有益的技术参考。

UPLC-MS/MS法测定精油类化妆品中13种双酚类及烷基酚类环境激素

建立了一种超高效液相色谱-串联质谱(UPLC-MS/MS)方法测定精油类化妆品中13种双酚类及烷基酚类环境激素。精油类化妆品以10%的氨水-乙腈溶液超声提取,氮吹浓缩后,以甲醇和水流动相梯度洗脱,经Agilent Poroshell EC-C18(3.0×150 mm,2.7μm)色谱柱分离,电喷雾离子源负离子模式(ESI-)扫描,多反应监测模式(MRM)定量分析。结果表明,13种双酚类及烷基酚类环境激素在0.25~200 ng/m L中一定质量浓度范围内呈现良好线性关系,线性相关系数均大于0.99,各物质检出浓度(LOD)为0.000375~0.0075μg/g,定量浓度(LOQ)为0.00125~0.025μg/g;在0.025,0.05及0.25μg/g三种不同加标浓度水平下,各物质平均回收率范围为81.8%~113.4%,日内精密度(n=6)为1.1%~8.5%,日间精密度(n=18)为3.5%~11.5%,方法前处理过程简单、回收率好、稳定性高,实现了13种目标物质的有效色谱分离,适用于精油类化妆品中13种双酚类及烷基酚类环境激素的同时定量定性分析。

环境水体中烷基酚前处理技术研究进展

烷基酚化合物作为一类典型的环境内分泌干扰物,可在水环境中长期稳定存在,已成为国内外众多学者研究的焦点之一。通过调研近年来国内外环境水体中烷基酚污染状况,针对其前处理技术进行了综述,重点介绍了环境水体中烷基酚分析检测过程中常用的液液萃取、固相萃取、固相微萃取等前处理技术的原理、特点、影响因素及应用范围等。经梳理和分析相关文献,得出以下结论:1)烷基酚在国内外各类水环境介质中被广泛检出,浓度范围一般为未检出(ND)~几千ng/L,易吸附在水中悬浮物或胶体颗粒上,亟须建立可靠、高效、快速的前处理技术,为其在水体中的准确定性和定量分析奠定良好的基础;2)与固相微萃取和搅拌棒吸附萃取相比,液液萃取技术和固相萃取技术在回收率、精密度和稳定性方面更具优势,已被多个国家应用于水质烷基酚的标准分析方法中。未来应加强填料萃取容量和选择性、涂层耐用性、多种萃取技术联用等方面研究,以建立快速高效、微型化、无溶剂或少溶剂化、对环境友好、自动化的前处理技术;加强烷基酚化合物的管理,建议将其纳入水质质量标准、排放标准等。