Determination of nonylphenol and nonylphenol ethoxylates in environmental solid samples by ultrasonic-assisted extraction and high performance liquid chromatography-fluorescence detection

A simple and rapid analytical method for the determination of nonylphenol (NP) and nonylphenol ethoxylates (NPEOx) in solid environmental samples has been developed. This method combines an ultrasonic-assisted extraction procedure in small columns and an enrichment step onto C(18) solid-phase extraction cartridges prior to separation using HPLC with fluorescence detection. Method optimization was carried out using soil samples fortified at different concentration levels (from 0.1 to 100 microg/g). Under optimum conditions, 2g of soil was placed in small glass columns and extraction was performed assisted by sonication (SAESC) at 45 degrees C in two consecutive steps of 15 min using a mixture of H(2)O/MeOH (30/70). The obtained extracts were collected, loaded onto 500 mg C(18) cartridges, and analytes were eluted with 3 x 1 ml of methanol and 1 ml of acetonitrile. Finally, sample extracts were evaporated under a nitrogen stream, redissolved in 500 microl H(2)O/AcN (50/50), and passed though a 0.45 microm nylon filter before final determination by HPLC-FL. The developed procedure allowed to achieve quantitative recoveries for NP and NPEOx, and was properly validated. Finally, the method was applied to the determination of these compounds in soils and other environmental solid samples such as sediments, compost and sludge.     

Simultaneous determination of degradation products of nonylphenol polyethoxylates and their halogenated derivatives by solid-phase extraction and gas chromatography-tandem mass spectrometry after trimethylsilylation

An efficient method for the simultaneous determination of the degradation products of nonylphenol polyethoxylates (NPnEOs, n = number of ethoxy units), i.e., nonylphenol (NP), NPnEOs (n = 1-3), nonylphenoxy carboxylic acids (NPnECs, n = 1-2, number of ethoxy units plus an acetate) and their halogenated derivatives (XNP, XNP1EO and XNP1EC; X = Br or Cl), in water samples were developed. After trimethylsilylation with N,O-bis(trimethysilyl)acetamide, all the analytes were determined by gas chromatography-tandem mass spectrometry (GC-MS-MS) with electron ionization (EI). The ion peaks of [M - 85]+ of the derivatives were selected as precursor ions and their product ions showing the highest intensities were used for the quantitative analysis. The instrumental detection limits were in the range from 2.1 to 11 pg. The recoveries of the analytes from the water samples were optimized by using solid-phase extraction (SPE). The deuterated reagents of octylphenol, octylphenol monoethoxylate and octylphenoxyacetic acid were used as the surrogates. The method detection limits (500 ml water sample) using C18 SPE were from 2.5 to 18 ng/l. The recoveries from spiked pure water and the environmental water samples were greater than 78%. The method was successfully applied to environmental samples. Remarkably, the concentrations of the halogenated compounds (CINP, CINP1EO and BrNP1EO) were detected at the hundreds of ng/l levels in the Neya river.     

Rotating-disk sorptive extraction of nonylphenol from water samples

In this study the sorption of nonylphenol was implemented on a rotating Teflon disk coated with a PDMS film on one of its surfaces. In this way, the disk, which has a high surface area, contacts only the liquid sample, which can be stirred at higher velocity than with the stir bar used in stir-bar sorptive extraction (SBSE), without damaging the phase while at the same time facilitating analyte mass transfer to the PDMS surface. We refer to the procedure as rotating-disk sorptive extraction (RDSE). Extraction variables such as disk rotational velocity, extraction time, and surface area of PDMS film were studied to establish the best conditions for extraction. With increasing rotational velocity, the amount of extracted analyte significantly increases because the stagnant layer concomitantly decreases. On the other hand, the extracted amount concomitantly increases with extraction time, reaching equilibrium at approximately 20 min, which can be reduced to 10 min when the surface area of PDMS increases from 1.74 to 6.97 cm². Precision of the method was determined by using the same disk (n = 6) and different disks (n = 3), showing relative standard deviations for the analyte of 3.7% and 10%, respectively. The detection limit of the method was 0.09 μg/L NP, defined at a signal to noise ratio of 3. The method was applied to a real sample, achieving quantitative recovery. The PDMS phase on the disk could be used for at least 50 experiments. In any case, replacement of the PDMS film on the disk is very easy and inexpensive, as compared to the commercial alternative SBSE.     

Separation of nonylphenol ethoxylates and nonylphenol by non-aqueous capillary electrophoresis

Capillary electrophoresis based on non-aqueous solvent background electrolytes was employed, with single and multiple wavelength UV detection, to evaluate discrimination among oligomer components of mixtures of non-ionic, long chain nonylphenol ethoxylates (NPnEO, with n = number of ethoxy units) and their lipophilic degradation products. The tested organic solvents included acetonitrile, methanol, ethanol, 1- and 2-propanol, 1-butanol and tetrahydrofurane in the presence of sodium acetate. A rational variation of composition of background electrolyte solvent mixtures allowed to modify the mobility of electroosmotic flow and the type and degree of interactions between the ionic additive (sodium acetate) and the components of the analyte mixtures. The physicochemical properties of the solvents, such as dielectric constant, viscosity and electron donor-acceptor ability regarding the additive, were considered to improve the resolution of lipophilic compounds with less than three ethoxy groups and the discrimination attainable for longer chain oligomers. The studied methodologies also allowed discerning between surfactants of similar (nominal) ethoxy chain lengths. This was demonstrated by the different peak distribution patterns observed for NPnEO compounds with n = 7.5 and 10, respectively.     

Molecularly imprinted polymer for selective extraction of endocrine disrupters nonylphenol and its ethoxylated derivates from environmental solids

Nonylphenol isomers (NP), linear nonylphenol (4-n-NP) and NP short chain ethoxylated derivates (NPEO1 and NPEO2) are degradation products of nonylphenol polyethoxylates, a worldwide used group of surfactants. All of them are considered endocrine disrupters due to their ability to mimic natural estrogens. In this paper, the preparation and evaluation of several 4-n-NP molecularly imprinted polymers (MIPs) for the selective extraction and clean-up of 4-n-NP, NP, NPEO1 and NPEO2 from complex environmental solid samples is described. Among the different combinations tested, a methacrylic acid-based imprinted polymer prepared in toluene provided the better performance for molecularly imprinted SPE (MISPE). Under optimum MISPE conditions, the polymer was able to selectively retain not only linear NP but also the endocrine disruptors NPEO1, NPEO2 and NP with recoveries ranging from 60 to 100%, depending upon the analyte. The developed MISPE procedure was successfully used for the determination of 4-n-NP, NP, NPEO1 and NPEO2 in sediments and sludge samples at concentration levels according to data reported in the literature for incurred samples. Finally, various sludge samples collected at five different sewage treatment plants from Madrid and commercial sludge for agriculture purposes were analysed. The measured concentrations of the different compounds varied from 3.7 to 107.5 mg/kg depending upon the analyte and the sample.     

Photometric extraction method for determination of oxacillin and its derivatives

Microchimica Acta - A new extraction photometric method is developed for determination of oxacillin and its chlorinated derivates, based on the extraction of ion-pairs of the oxacillin anion and...     

Liquid-liquid extraction of some actinides with polyethyleneglycol and its derivatives

Polyethyleneglycol (PEG) and its derivatives of high molecular weight were found to be employed as useful extractants for the solvent extraction of uranium. The extraction behaviors of uranium and neptunium were investigated, particularly concerning the dependence of the extractibility of uranium(VI) on the molecular weight of PEG. A dominating species of the extracted uranium(VI) thiocyanate complexes was assumed to be NH₄ UO₂(SCN)₃·(PEG). The extraction of protactinium was also preliminarily studied. The extraction of these actinides from an acidic thiocyanate solution increased in the order: uranium(VI)>protactinium(V)>neptunium(V).     

Identification of photocatalytic degradation products of non-ionic polyethoxylated surfactants in wastewaters by solid-phase extraction followed by liquid chromatography-mass spectrometric detection

The photodegradation of non-ionic surfactants (nonylphenol- and alcohol-polyethoxylates, NPEO_x and C_nEO_x) was investigated in different waters with and without a photoinducter (Fe(III)). Deionized water and industrial effluent spiked at 0.5 mg/L with C₁₀EO₆ and NPEO₉ were irradiated using a xenon arc lamp. Aliquots of the test solutions were taken at different time intervals and were preconcentrated using solid phase extraction (SPE) with C₁₈ cartridges. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) was used to identify the chemical species generated from phototransformation of non-ionic surfactants. 2 ) and nonylphenol ethoxy acetic acid (NPE₂C). Much smaller amounts of degradation products of NPEO₉ having only the alkyl chain carboxylated were also formed in the photocatalysis experiment. The identified C₁₀EO₆ photoproducts included fatty alcohols and acids. Polyethylene glycols (PEGs) were also formed as the consequence of the central scission of C₁₀EO₆ and the deethoxylation of NPEO₉. The photodegradation in wastewater samples was more efficient than in deionized water being the half-life (t_1/2) of C₁₀EO₆, 48 h and 29 h in deionized water and wastewater, respectively, and for NPEO₉, 17 h and 14 h in deionized water and wastewater, respectively. When induced photodegradation was undertaken, the t_1/2 for NPEO₉ was 21 min and 29 min in deionized water and wastewater, respectively. Disappearance of parent compounds was observed after 120 h from the beginning of the photodegradation experiment, or after 210 min of irradiation for the photocatalysis. Received: 27 September 2000 / Revised: 11 January 2001 / Accepted: 14 January 2001     

Determination of non-ionic polyethoxylated surfactants in wastewater and river water by mixed hemimicelle extraction and liquid chromatography-ion trap mass spectrometry

The capability of hemimicelles-based solid phase extraction (SPE)/liquid chromatography/atmospheric pressure chemical ionisation in positive mode, ion trap mass spectrometry (LC/(APCl+-IT)-MS) for the concentration, separation and quantitation of non-ionic surfactants has been investigated. Concentration was based on the formation of mixed aggregates of analytes [alkylphenol ethoxylates (APE, octyl and nonyl) and alkyl ethoxylates (AE, C12-C16)] with the anionic surfactant sodium dodecyl sulphate (SDS) that is adsorbed on alumina. Parameters affecting SPE were investigated on the basis that hemimicelles are dynamic entities in equilibrium with the aqueous phase. The performance of ion trap mass spectrometry for MS and MS/MS quantitation of non-ionic homologues was assessed. Recoveries of analytes from wastewater influent and effluent and river water samples ranged between 91 and 98% and were found independent on the length of the alkyl chain under the optimised conditions. Anionic surfactants did not interfere to the levels found in environmental samples. The detection limits ranged between 14 and 111 ng/l for wastewater influent, 10 and 40 for wastewater effluent and 4 and 35 for river water, after concentration of 250, 500 and 750 ml of sample, respectively. The approach was applied to the determination of AE and APE in influent and effluent samples from four wastewater treatment plants and four river samples. The concentrations of individual non-ionic surfactants found ranged between 0.3 and 373 microg/l.     

Identification of photocatalytic degradation products of non-ionic polyethoxylated surfactants in wastewaters by solid-phase extraction followed by liquid chromatography-mass spectrometric detection

The photodegradation of non-ionic surfactants (nonylphenol- and alcohol-polyethoxylates, NPEOx and CnEOx) was investigated in different waters with and without a photoinducter (Fe(III)). Deionized water and industrial effluent spiked at 0.5 mg/L with C10EO6 and NPEO9 were irradiated using a xenon arc lamp. Aliquots of the test solutions were taken at different time intervals and were preconcentrated using solid phase extraction (SPE) with C18 cartridges. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) was used to identify the chemical species generated from phototransformation of non-ionic surfactants. The intermediates detected included nonylphenol diethoxylate (NPEO2) and nonylphenol ethoxy acetic acid (NPE2C). Much smaller amounts of degradation products of NPEO9 having only the alkyl chain carboxylated were also formed in the photocatalysis experiment. The identified C10EO6 photoproducts included fatty alcohols and acids. Polyethylene glycols (PEGs) were also formed as the consequence of the central scission of C10EO6 and the deethoxylation of NPEO9. The photodegradation in wastewater samples was more efficient than in deionized water being the half-life (t(1/2)) of C10EO6, 48 h and 29 h in deionized water and wastewater, respectively, and for NPEO9, 17 h and 14 h in deionized water and wastewater, respectively. When induced photodegradation was undertaken, the t(1/2) for NPEO9 was 21 min and 29 min in deionized water and wastewater, respectively. Disappearance of parent compounds was observed after 120 h from the beginning of the photodegradation experiment, or after 210 min of irradiation for the photocatalysis.     

Solid-phase extraction preconcentration of 2,4-dichlorophenoxyacetic acid on silica with immobilized polyethoxylated isooctylphenol groups

Silica with immobilized polyethoxylated isooctylphenol groups (SiO ₂ -TX) is studied as an adsorbent for the solid-phase extraction preconcentration of pesticides based on chlorophenoxyalkanecarboxylic acids from aqueous solutions. It is demonstrated that 2,4-dichlorophenoxyacetic acid (2,4-D) is efficiently (up to 96%) extracted as an ion associate with cetyltrimethylammonium bromide (CTMAB) with SiO₂-TX in the pH range 8–10. The optimum CTMAB-to-2,4-D molar ratio is 200: 1. The capacity of SiO₂-TX to 2,4-D in the Henry region is 0.42 mg/g of adsorbent, and the distribution coefficients reach 9 × 10² mL/g. It is shown that 2,4-D is quantitatively eluted with 1–2 mL of acetonitrile, which allowed us to use the adsorbent in a preconcentration cartridge before determining pesticides by HPLC. The procedure allowed pesticides to be recovered from aqueous solutions in concentrations beginning from 0.025 mg/L.     

Determination of nonylphenol and nonylphenol ethoxylates in pulp samples by Py-GC/MS

We have developed a method for ascertaining the presence of nonylphenol (NP) and nonylphenol ethoxylates (NPEs) in pulp samples at very low levels. The method entails pre-concentration of the compounds and their detection by Py-GC/MS. Solvent extraction of the compounds from pulps with acetone gives better recoveries than desorption of the compounds from the pulps by gas stripping. The detection limit for NPEs with our technique is as low as 0.003 ppm in pulp sheets.     

Determination of nonylphenol and octylphenol in paper by microwave-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry

A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography-mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25-125 microg kg(-1) for OP and 9.50-950 microg kg(-1) for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56 microg kg(-1) for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211 microg kg(-1).     

Theoretical study of mechanism of extraction reaction between germylene carbene and its derivatives and thiirane

The mechanism of the sulfur extraction reaction between singlet germylene carbene and its derivatives [X₂Ge?C: (X = H, F, Cl, CH₃)] and thiirane has been investigated with density functional theory, including geometry optimization and vibrational analyses for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by B3LYP/6‐311G(d,p) method. From the potential energy profile, it can be predicted that the reaction pathway of this kind consists two steps: (1) the two reactants firstly form an intermediate (INT) through a barrier‐free exothermic reaction; (2) the INT then isomerizes to a product via a transition state (TS). This kind reaction has similar mechanism, when the germylene carbene and its derivatives [X₂Ge?C: (X = H, F, Cl, CH₃)] and thiirane get close to each other, the shift of 3p lone electron pair of S in thiirane to the 2p unoccupied orbital of C in X₂Ge = C: gives a p → p donor–acceptor bond, leading to the formation of INT. As the p → p donor–acceptor bond continues to strengthen (that is the C? S bond continues to shorten), the INT generates product (P + C₂H₄) via TS. It is the substituent electronegativity that mainly affects the extraction reactions. When the substituent electronegativity is greater, the energy barrier is lower, and the reaction rate is greater. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Calculation of hydrophile-lipophile balance for polyethoxylated surfactants by group contribution method

Based on Davies' group contribution method, hydrophile-lipophile balance (HLB) values were calculated by effective chain length (ECL) instead of actual chain length of straight alkyl chain, polyoxyethylene (EO) chain, and polyoxypropylene (PO) chain. Linear equations were adopted for the effective chain length of straight alkyl chain and PO chain; a Gamma probability density function (PDF) was used to describe the contribution of each EO group to HLB and the effective chain length of EO chain could be obtained by integrating Gamma PDF. The HLB values of 224 nonionic surfactants were calculated and the average absolute error is less than 1.5, which is much better than the results obtained by Davies.     

A study of polyethoxylated alkylphenols by packed column supercritical fluid chromatography

Alkylphenol polyethoxylates (APEs) are a widely used group of nonionic surfactants in commercial production. Characterization of the composition of APE mixtures can be exploited for the determination of their most effective uses. In this study sample mixtures contain nonylphenol polyethoxylates and octylphenol polyethoxylates. The separation of individual alkylphenols by ethoxylate units is performed by supercritical fluid chromatography (SFC)-UV as well as normal-phase high-performance liquid chromatographic (HPLC)-UV employing packed columns. The stationary phase and column length are varied in the SFC setup to produce the most favorable separation conditions. Additionally, combinations of packed columns of different stationary phases are tested. The combination of a diol and a cyano column is found to produce optimal results. An advantage of using packed columns instead of capillary columns is the ability to inject large amounts of sample and thus collect eluted fractions. In this regard, fractions from SFC runs are collected and analyzed by flow injection analysis-electrospray ionization-mass spectroscopy in order to positively identify the composition of the fractions. In comparing the separation of APE mixtures by SFC and HPLC, it is found that SFC provides shorter retention times with similar resolution. In addition, less solvent waste is produced using SFC.     

Determination of nonylphenol and nonylphenol ethoxylates in wastewater using MEKC

Nonylphenol ethoxylates (NPEO_x) are surfactants which are used worldwide and can be transformed in the environment by microorganisms to form nonylphenol (NP). Analysis of these compounds was carried out with micellar electrokinetic capillary chromatography (MEKC). Different parameters such as background electrolyte (BGE) solution, pH, type of surfactant, and sample stacking were optimized. The use of CHES (20 mM, pH 9.1) in combination with 50 mM sodium cholate as a surfactant as BGE solution, together with sample stacking using 50 mM NaCl in the sample and an injection time of 20 s, provided the best separation of the compounds studied. The method was applied to the determination of target analytes in two types of sludge water coming from two steps of a wastewater treatment plant. Liquid–liquid extraction was carried out using toluene as solvent, resulting in recoveries around 100% for all studied analytes. The presence of NPEO_x was observed in the first step of the sludge water treatment, based on migration time and UV spectra. Identification was confirmed using tandem MS. LOQs of the studied compounds were in the range of 12.7 to 30.8 ng/mL, which is satisfactory for the analysis of real wastewater samples.     

Interaction of asphaltenes with nonylphenol by microcalorimetry

This paper shows the work performed in the study of the capability of isothermal titration calorimetry (ITC) to characterize the interaction between petroleum asphaltenes with a model molecule, namely, nonylphenol. ITC is widely used in biochemistry to study the interaction of proteins with ligands. The intention is to transfer the knowledge into the asphaltene field, with the aim of getting a better understanding of the mechanism of interaction, as well as the energies involved in this process. Calorimetric experiments show that nonylphenol has a complex mechanism of interaction with asphaltenes in toluene, including more than one process. Several models have been used to fit the experimental data. The enthalpies calculated with a model based on polymerization are in the order of -1 to -7 kJ/mol, which are very close to the hydrogen bond energies. This shows the capability of ITC to provide experimental data to the modeling of asphaltene behavior. The number of sites of interaction has been inferred by means of a model taken from protein-ligand science. The values obtained are in the range two to five sites per molecule, assuming an average Mw of 1000 units.     

Analysis of nonylphenol and nonylphenol ethoxylates in environmental samples by mixed-mode high-performance liquid chromatography-electrospray mass spectrometry.

A new method is described based on mixed-mode high-performance liquid chromatography with electrospray mass spectrometry detection for comprehensive quantitative analysis of nonylphenol (NP) and nonylphenol ethoxylates (NPEOs) in wastewater and sediment. Efficient separation, reduced band broadening, and high sensitivity were achieved by employing a methanol-water gradient on a mixed-solvent gel filtration column designed for MS interfacing. Quantitative accuracy and precision of the method were improved by the use of custom-synthesized [13C6]NPEO analogs as isotope-dilution surrogate standards. Method detection limits for NP and individual NPEOs ranged from I to 55 pg injected on column.