Determination of a non-ionic surfactant in aqueous environmental samples by flow-injection analysis with chemiluminescence detection

A flow-injection procedure for the determination of a commercially available fatty amine ethoxylate-based non-ionic surfactant in sea water over the range 0–50 mg l^?1 is described. The procedure is based on measurement of the chemiluminescence emission resulting from oxidation of the tertiary amine group with sodium hypochlorite at pH 10.5 in the presence of Rhodamine B, which acts as a sensitizer.     

Micro-pumping flow system for spectrophotometric determination of anionic surfactants in water

A novel procedure has been developed for spectrophotometric determination of anionic surfactants in water using a solenoid micro-pump as fluid-propulsion device. The proposed method is based on substitution of methyl orange (MO) by anionic surfactants in the formation of an ion-pair with the cetyl pyridine ion (CPC⁺) at pH 5.0. The flow network comprised four solenoid micro-pumps which, under microcomputer control, enabled sample and reagent introduction, and homogenisation in the reaction zone. The system is flexible and simple to operate and control, and sensitive and precise. The analytical plot for the anionic surfactant was linear between 1.43×10^–6 and 1.43×10^–5 mol L^–1 (0.5 to 5.0 mg L^–1; R=0.997, n=5). The relative standard deviation was 0.8% (n=11) for a sample containing 5.74×10^–6 mol L^–1 (2 mg L^–1) surfactant. The limit of detection was 9.76×10^–8 mol L^–1 (0.034 mg L^–1) and the sampling throughput was 60 determinations per hour. The results obtained for washing-water samples were comparable with those obtained by use of the reference method, and no significant differences at the 95% confidence level were observed.     

Adsorption of surfactants on low-charged layer silicates Part II: Adsorption of non-ionic surfactants

Nonionic surfactants were adsorbed on low-charged layer silicates in the interlayers. After drying, the surfactants were arranged in densely packed double layers. However, in suspension considerably higher basal spacings are measured by x-ray diffraction which indicate that large quantities of non-ionic surfactants are adsorbed. With the aid of calorimetry, enthalpies of displacement were recorded which suggest strong interactions of the non-ionic surfactants with smectites. In analogy to tests on hydrophilic SiO₂, the adsorption of smectites is found to depend on the degree of ethoxylation of the non-ionic surfactant. The adsorption declines with increasing EO content.List of symbols n ^s adsorbed amount of surfactants (mmol/g) - n _max ^s maximal adsorbed amount of surfactants - d _L basal spacing (nm) - d _L interlayer separation because of adsorption - V _M molar volume of surfactant - V _max ^s volume of adsorbed surfactants (cm³/g) - V _int volume between the silicate layers (interlayer volume) (cm³/g) - H enthalpy of displacement (J/g) - h _max max. molar enthalpy of displacement (kJ/mol) Part I: Prog. Colloid Polymer Sci. 84, 206This paper is part of W. Röhl's doctorial dissertation at the Heinrich-Heine University, Düsseldorf     

Surface activity and micellar properties of anionic gemini surfactants and their analogues

The properties of didodecyldiphenylether disulfonate gemini-type surfactants have been studied and compared to mono-alkylated and monosulfonated analogous surfactants. Dynamic and equilibrium surface tension measurements indicate that the gemini surfactants have a higher surface activity compared to that of the monoalkyl analogues. The gemini-type surfactants have much larger surface area per molecule, opposite effect of carbon number on CMC and considerable swelling of the micelles upon increasing surfactant concentration. Determination of aggregation numbers by fluorescence measurements reveals that the longer chain gemini surfactants form micelles having less than 10 molecules per micelle.     

离子色谱-质谱联用技术测定饮用水及环境水样中的痕量高氯酸盐

建立了一种测定痕量高氯酸盐的离子色谱-质谱联用方法.选用高容量、强亲水性的阴离子交换柱IonPac AS20(2 mm)进行分离,以淋洗液自动发生器在线产生的KOH为淋洗液,采用等浓度淋洗.在不添加有机溶剂的情况下,淋洗液经过抑制器抑制后直接进入电喷雾-串联质谱(ESI-MS-MS),以负离子模式进行检测.同时采用多元反应监测(MRM)模式对高氯酸盐进行监控,以100.8/84.9、 98.8/66.9和100.8/68.9为监控离子对,以98.8/82.9离子对的峰面积进行定量.高氯酸盐质量浓度在0.05～50 μg/L范围内具有良好的线性(r＝0.9985),检出限(S/N=3)为0.01 μg/L.将该方法用于饮用水以及地下水、雪水等环境水样中高氯酸盐的分析,并进行了加标回收实验,回收率在86%～110%之间,将实际自来水样品连续11次进样,所得高氯酸盐的峰面积的相对标准偏差(RSD)为1.6%.     

Separation and determination of non-ionic surfactants of the nonylphenol polyglycol ether type by liquid chromatography

A normal-phase method for the separation and determination of non-ionic surfactants of the 4-nonylphenol polyglycol ether (NPEO) type by liquid chromatography is described, based on a LiChrosorb-Diol column and nonpolar linear gradient elution, with spectrophotometric detection at 275 nm. The method was applied to the determination of NPEO oligomers in the technical surfactants Arkopal N-20, N-40, N-60 and N-100 and in aqueous solutions from flotation processes. The relative standard deviations were 2.47–5.62%. The detection limits for nonylphenol polyglycol ether with 2, 4, 6, 8, 10, 13 and 15 ethoxy units were 51, 57, 64, 74, 85, 118 and 132 ng, respectively. The method can also be used for the determination of other alkylphenol polyglycol ethers. Reversed-phase LC with an octadecylsilica column was investigated and can be applied to the identification of the alkyl group present.     

Determination of anionic surfactants by bis(ethylenediamine)copper(II) extraction and anodic stripping voltammetry

A stripping voltammetric finish for the measurement of total anionic surfactant has been developed. A limit of detection of 5.0 μg 1^?1 anionic surfactant was observed with a linear calibration from 5.0 to 500 μg 1^?1 in the original sample.     

Studies on the electrocapillary curves of anionic surfactants in presence of non-ionic surfactants

Polyoxyethylated non-ionic surfactants such as Tween 20, Tween 40, Nonidet P40 and Nonex 501 have been supposed to be associated with cationic characteristics. Studies on the effect of these surfactants on the electrocapillary curves of the anionic surfactants Aerosol IB, Manaxol OT and sodium lauryl sulphate (SLS), show that the electrocapillary maxima shift towards positive potentials. The order of adsorption of the anionic surfactants is SLS > Manaxol OT > Aerosol IB while the shift in maxima is in the order Aerosol IB ~ Manaxol OT > SLS which confirms association of cationic characteristics with the micelles of these non-ionic surfactants. The magnitude of the shift in electrocapillary maxima is Nonex 501 > Nonidet P40 > Tween 20 > Tween 40 which may be the order of magnitude of the positive charge carried by these non-ionic surfactants.     

Deposition and release of chlorhexidine from non-ionic and anionic polymer matrices

Therapeutic activity of locally applied drugs depends on both the thermodynamic activity of the active molecule and the pharmaceutical system which enables the release of the molecule; also the vasoconstrictive activity of vessels plays an important role. In this study, the release of chlorhexidine was assessed considering the use of ionic and non-ionic polymeric carriers at temperatures in the range between 22°C and 42°C, including the temperature of 32°C as the reference surface body temperature. The obtained release rates and concentrations of chlorhexidine, loaded to methylcellulose and poly(acrylic acid) gels, were compared with respective viscositiy, pH, and conductivity of the assessed systems. The deposition patterns of chlorhexidine in the polymeric matrix were studied using energy dispersive X-ray spectrometry to evaluate the possible influence of chlorhexidine distribution in/on the carrier on the respective release rates. This study is significant for patients with various skin temperature conditions, who are required to receive local biocides applied on skin or into the oral cavity. The obtained precipitate of polyacrylic acid-chlorhexidine preparation was extensively studied to evaluate the chlorhexidine release and to develop an application in skin and dental care.     

Development and validation of an SPE methodology combined with LC-MS/MS for the determination of four ionophores in aqueous environmental matrices

A multi-residue analytical methodology has been established for the determination of the four ionophores: lasalocid, monensin, salinomycin and narasin in aqueous environmental matrices, using nigericin as internal standard. The samples were filtrated prior to solid phase extraction. All compounds were measured using liquid chromatography coupled to tandem mass spectrometry applying electro spray ionisation. The absolute recoveries ranged from 92 to 110% (relative standard deviation: 2–14%) for spiked river water. The final method allowed for detection of ionophores down to a few ng/L in natural water bodies with LOQs for the entire methodology being 40, 49, 67, and 14 ng/L for lasalocid, monensin, salinomycin, and narasin, respectively.     

Occurrence,fate and removal efficiencies of pharmaceuticals in wastewater treatment plants (WWTPs) discharging in the coastal environment of Algiers

In the last few decades, the presence of pharmaceutical products in the environment is known under the name of emerging contaminants. These substances can enter the aquatic environment via different sources, as parent compounds, metabolites or a combination of both. In this work, we have investigated the presence of four pharmaceutical active compounds belonging to the group of Non-Steroidal Anti-Inflammatory Drugs (NSAIDs), in wastewater, surface water and drinking water of Algiers, which have a direct impact on the Mediterranean Sea. The target analytes (ibuprofen (IBU), naproxen (NAP), ketoprofen (KET), and diclofenac (DIC)), were extracted from the water samples by using Solid Phase Extraction Oasis^® HLB Cartridges; the identification and quantification were realized by Gas Chromatography–Mass Spectrometry (GC–MS). To obtain the best resolution and precision, N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA) was used as the derivatization reagent and ibuprofen-d₃ was used as the internal standard. The obtained recoveries were good, ranging from 82% for ketoprofen to 120% for naproxen with relatively small standard deviations (≤20%). The target compounds were detected in wastewater, influent/effluent with concentrations ranging from 155.5 to 6554 ng/L, implicating removal efficiencies of wastewater treatment plants (WWTPs), between 30.3 and 95%. The surface water was also contaminated with pharmaceuticals from 72.9 ng/L for diclofenac to 228.3 ng/L for naproxen. In addition, the occurrence of ibuprofen and ketoprofen in drinking water, at concentrations of 142.1 and 110.9 ng/L, respectively, attracts concerns about possible impacts on human health.     

Extractive spectrophotometric determination of non-ionic surfactants in water

The solvent extraction of non-ionic surfactants with potassium chloride and tetrabromophenolphthalein ethyl ester potassium salt has been studied, and a method developed for determining trace amounts of non-ionic surfactants in water spectrophotometrically. Various non-ionic surfactants of general type RO(CH(2)CH(2)O)(n)H (where R is an alkyl or alkylphenyl group and n is the number-average degree of polymerization) are extracted quantitatively into o-dichlorobenzene from the water sample, and reacted in the organic phase with tetrabromophenolphthalein ethyl ester potassium salt to give a coloured product, the absorbance of which is measured at 620 nm.     

Analysis of nitrosamines in water by automated SPE and isotope dilution GC/HRMS Occurrence in the different steps of a drinking water treatment plant, and in chlorinated samples from a reservoir and a sewage treatment plant effluent

A method based on automated solid-phase extraction (SPE) and isotope dilution gas chromatography/high resolution mass spectrometry (GC/HRMS) has been developed for the analysis of nine nitrosamines in water samples. The combination of automated SPE and GC/HRMS for the analysis of nitrosamines has not been reported previously. The method shows as advantages the selectivity and sensitivity of GC/HRMS analysis and the high efficiency of automated SPE with coconut charcoal EPA 521 cartridges. Low method detection limits (MDLs) were achieved, along with a greater facility of the procedure and less dependance on the operator with regard to the methods based on manual SPE. Quality requirements for isotope dilution-based methods were accomplished for most analysed nitrosamines, regarding to trueness (80–120%), method precision (<15%) and MDLs (0.08–1.7 ng/L).Nineteen water samples (16 samples from a drinking water treatment plant {DWTP}, 2 chlorinated samples from a sewage treatment plant {STP} effluent, and 1 chlorinated sample from a reservoir) were analysed. Concentrations of nitrosamines in the STP effluent were 309.4 and 730.2 ng/L, being higher when higher doses of chlorine were applied. N-Nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA) were the main compounds identified in the STP effluent, and NDEA was detected above 200 ng/L, regulatory level for NDMA in effluents stated in Ontario (Canada). Lower concentrations of nitrosamines were found in the reservoir (20.3 ng/L) and in the DWTP samples (n.d. −28.6 ng/L). NDMA and NDEA were respectively found in the reservoir and in treated and highly chlorinated DWTP samples at concentrations above 10 ng/L (guide value established in different countries). The highest concentrations of nitrosamines were found after chlorination and ozonation processes (ozonated, treated and highly chlorinated water) in DWTP samples.     

Determination of nine emerging pesticides at trace level in aqueous samples using fully automated on-line solid phase extraction coupled with liquid chromatography-mass spectrometry

On-line solid phase extraction (SPE) coupled to liquid chromatography-mass spectrometry (LC-MS) offers an easy and fast strategy to analyze the organic contaminants in environmental samples with high sensitivity and selectivity. This paper described an in-house designed on-line SPE system and an on-line SPE-LC-MS method for the determination of pesticides at trace levels in water samples. The system was assembled from an eight-position valve, a piston pump, a six-port valve and a C18 SPE column, and significantly reduced analysis time by achieving full automation. Moreover, the use of a large enrichment volume (50?mL) significantly enhanced method sensitivity. Using this on-line SPE system, an on-line SPE-LC-MS method was developed for the determination of nine pesticides at trace levels in lake water and seawater sample. Under optimized conditions, method detection limits (MDLs) were 1.00–10.0?ng?L^?1.     

Sorption-photometric determination of anionic surfactants in water

The adsorption of Crystal Violet, anionic surfactants, and their ion associates on nonionic hydrophobic polymer adsorbent Amberlite XAD-16 was studied. A procedure for the sorption-photometric determination of anionic surfactants in water was developed with a detection limit of 0.001–0.003 mg/L at a sample volume of 50 mL.     

A multicommuted stop-flow system employing LEDs-based photometer for the sequential determination of anionic and cationic surfactants in water

It has been developed an automatic stop-flow procedure for sequential photometric determination of anionic and cationic surfactants in a same sample of water. The flow system was based on multicommutation process that was designed employing two solenoid micro-pumps and six solenoid pinch valves, which under microcomputer control carry out fluid propelling and reagent solutions handling. A homemade photometer using a photodiode as detector and two light emitting diodes (LEDs) with emission at 470 nm (blue) and 650 nm (red) as radiation sources, which was tailored to allow the determination of anionic and cationic surfactants in waters. The procedure for anionic surfactant determination was based on the substitution reaction of methyl orange (MO) by the anionic surfactant sodium dodecylbenzene sulfonate (DBS) to form an ion-pair with the cetyl pyridine chloride (CPC). Features such as a linear response ranging from 0.35 to 10.5 mg L⁻¹ DBS (R = 0.999), a detection limit of 0.06 mg L⁻¹ DBS and a relative standard deviation of 0.6% (n = 11) were achieved. For cationic surfactant determination, the procedure was based on the ternary complex formation between cationic surfactant, Fe(III) and chromazurol S (CAS) using CPC as reference standard solution. A linear response range between 0.34 and 10.2 mg L⁻¹ CPC (R = 0.999), a detection limit of 0.05 mg L⁻¹ CPC and a relative standard deviation of 0.5% (n = 11) were obtained. In both cases, the sampling throughput was 60 determinations per hour. Reagents consumption of 7.8 μg MO, 8.2 μg CPC, 37.2 μg CAS and 21.6 μg Fe(III) per determination were achieved. Analyzing river water samples and applying t-test between the results found and those obtained using reference procedures for both surfactant types provide no significant differences at 95% confidence level.     

Determination of anionic surfactants in lubrication fluids

A simple method is described for the isolation and determination of anionic surfactants in oils and emulsions used as lubricants in metal working processes. The oils were separated on silica gel solid phase extraction columsn by successive elution of solvents with increasing polarity as hexane, diisopropyl ether, acetic acid ethyl ester, acetone and methanol/NH₃ (8:1). The most polar methanol phase, which contains the surfactants, was titrated with Hyamine and the end point was determined potentiometrically using an ion sensitive electrode. The retention behaviour of sulfonates and sulfates on the sorbent has not been affected by other lubricants.     

离子缔合物-萃取荧光光度法测定水中阴离子表面活性剂

在 0 .2 5 mol/L H2 SO4 溶液中 ,罗丹明 B与阴离子表面活性剂形成离子缔合物 ,氯仿萃取后 ,于 5 5 0 nm处激发 ,荧光波长为 60 0 nm,对于十二烷基硫酸钠的线性范围为 0 .0 2 5～ 0 .4mg/L,RSD<2 .6%。方法可用于河水及生活废水中 1 0 -7～ 1 0 -6mol/L 阴离子表面活性剂的测定