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.

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.

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.

超高效液相色谱-串联质谱法测定土壤中烷基酚

A quick and sensitive analytical method for alkylphenols in soil was determined using accelerate solvent extraction and UPLC-MS/MS.It was determined that,analysis of one sample needed only 6 min.Recoveries of 4-tert-octylphenol,4-nonylphenol,4-octylphenol were 82.8%-104%,79.3%-98.4%,92.9%-109%,respectively,at the same time,the detection limit and area RSD were 0.001-0.005 mg/kg,2.0%-3.4%.

Determination of 4-nonylphenol and 4-tert-octylphenol compounds in various types of wastewater and their removal rates in different treatment processes in nine wastewater treatment plants of Iran

Alkylphenols(APs), considered as xenoestrogenic compounds, mainly exist as 4-nonylphenol(4-NP) and 4-tertoctylphenol(4-t-OP) in environments. The high stability and accumulation of APs in aquatic systems have caused endocrine disruption. In this study we measured APs in the wastewater influent and effluent samples, from the urban, rural, livestock, commercial and hospital wastewater treatment plants(WWTPs) in Iran. Dispersive liquid–liquid microextraction(DLLME) combined with gas chromatography–mass spectrometry(GC–MS) was used for the extraction and determination of 4-NP and 4-t-OP. In these treatment plants, various processes such as activated sludge, aerated lagoon, moving bed biofilm reactor and activated sludge along with wetland were applied. The highest concentration of 4-NP and 4-t-OP was observed in commercial and livestock sewages. The activated sludge along with wetland and then the MBBR process showed the highest removal rates of pollutants. The rates of biodegradability and accumulation in sludge were determined and also the specific adsorption coefficient Kdand the organic carbon–water partition coefficient kOCof the sludge for APs were calculated.

Research Development of Endocrine Disrupting Chemicals(EDCs) in Water in China

More and more importance has been attached to the problem of endocrine disrupting chemicals (EDCs) since 1960s. This article elaborates the recent research progress of EDCs in water and the trends in the near future in China.

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.

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.

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.

Toxicity of the xenoestrogen nonylphenol and its biodegradation by the alga Cyclotella caspia

Alkylphenols （APs）, the breakdown products of alkylphenol polyethoxylates that are widely used as surfactants, have been proven to exert estrogenic effects. With industrial development, higher concentrations of APs are discharged into aquatic environments. Nonylphenol （NP）, the most noxious AP, is included in the blacklist of several countries. The toxicity of NP to the alga Cyclotella caspia and the biodegradation of NP by C. caspia were studied in the laboratory. The median effective concentration at 96 hr （96 hr EC50 ） of NP for C. caspia was found to be 0.18 mg/L. Five toxicity and three degradation indices were selected for toxicity and biodegradation experiments, respectively, in five or three concentrations of NP set by the 96 hr EC50 of NP. The algal growth rate and chlorophyll a contents decreased as NP concentration increased. The main manifestations of morphological deformity of the cells included volume expansion and the presence of cytoplasmic inclusions （lipid droplets）. The abnormality rate of the cells increased with NP concentration and time, and was 100% at 0.22 and 0.26 mg/L of NP after 192 hr of culture. Superoxide dismutase activity initially increased and then declined at a higher NP toxicity of greater than 0.18 mg/L. After 192 hr of culture, the biodegradation rates of NP by C. caspia with initial concentrations of 0.14, 0.18, and 0.22 mg/L were 37.7%, 31.7%, and 6.5%, respectively. The kinetic equation of C. caspia biodegradation on NP was correlated with algal growth rate and initial NP concentration.