Amines In Water Samples Research Articles

Determination of trace amounts of aromatic amines after magnetic solid-phase extraction using silver-modified Fe3 O4 /graphene nanocomposite.

In this work, a fast and simple magnetic dispersive solid phase extraction methodology was developed utilizing Ag@magnetite nanoparticles@graphene nanocomposite as an efficient magnetic nanosorbent for preconcentration and determine of five aromatic amines in water samples. The sorbent was characterized by diverse characterization techniques. After the extraction, high-performance liquid chromatography with UV detection was utilized to analysis the aromatic amines. The effects of different factors on the extraction process were studied thoroughly via design of experiment and desirability function. Detection limits and linear dynamic ranges were obtained in the range of 0.10-0.20 and 0.3-300μg/L, respectively. The relative standard deviations (n=5) were in the range of 4.3-6.5%. Eventually, the method was employed for determination of target aromatic amines in various water samples.

Preparation and characterization of magnetic Wells–Dawson heteropoly acid nanoparticles for magnetic solid-phase extraction of aromatic amines in water samples

In this work, aminopropyl modified silica-coated magnetite nanoparticles with Wells–Dawson heteropoly acid (P2W17Fe@APSCMNPs) was first synthesized and underwent highly efficient magnetic solid-phase extraction (MSPE) of aromatic amines from aqueous samples. The resulted nanomaterials were characterized with different physicochemical techniques such as Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). Aniline, N,N-dimethylaniline, o-toluidine and 3-chloroaniline were selected as target compounds. The sample quantification was carried out using gas chromatography–flame ionization detector (GC–FID). Under optimal working conditions, the developed method showed good linearity (R>0.9912) in the range of 0.01–100ngmL−1. The method displays detection limits (at an S/N ration of 3) in the range from 0.003 to 0.01ngmL−1, and the limits of quantification (at an S/N ratio of 10) are between 0.01 and 0.04ngmL−1. The enrichment factors (EFs) were in the range of 75–113. Relative standard deviations (RSDs) are 4.8–8.3%. The applicability of the developed method was examined by analyzing different water samples (river water, tap water, well water and wastewater) and the relative recovery values for the spiked water samples were found to be in the range of 90.7–99.8%.

Combining different assays and chemical analysis to characterize the genotoxicity of waters impacted by textile discharges.

Waters receiving textile discharges can exhibit genotoxic and mutagenic activity, which has been related to the presence of dyes and aromatic amines as synthesis precursors or byproducts. The aim of this study was to identify dyes and aromatic amines in water samples impacted by textile discharges, and to evaluate the genotoxic responses of these samples using the Salmonella/microsome assay in strains TA98 and YG1041, and the Fpg-modified comet assay in the RTL-W1 fish cell line. The genotoxicity of river samples downstream of the discharge was greater than the upstream samples in both of the Ames tests. The Fpg-modified comet assay detected similar levels of DNA damage in the upstream and downstream samples. Mutagenicity was not detected with TA98, except for the Quilombo River samples, but when YG1041 was used as the tester strain mutagenicity was detected for all sites with a very different profile in upstream sites relative to the other sites. The mutagenic response strongly indicated that aromatic amines or dyes were contributing to the mutagenic activity downstream. The impact of textile discharges was also confirmed by chemical analysis, because the highest concentrations of azo dyes and aromatic amines were detected in the river downstream. This study shows the value of combining assays measuring complementary endpoints to better characterize the mutagenicity of environmental samples, with the advantage that this approach provides an indication of what classes of compounds are responsible for the effect. Environ. Mol. Mutagen. 57:559-571, 2016. © 2016 Wiley Periodicals, Inc.

Screening and Quantification of Aliphatic Primary Alkyl Corrosion Inhibitor Amines in Water Samples by Paper Spray Mass Spectrometry.

Direct analysis and identification of long chain aliphatic primary diamine Duomeen O (n-oleyl-1,3-diaminopropane), corrosion inhibitor in raw water samples taken from a large medium pressure water tube boiler plant water samples at low LODs (<0.1 pg) has been demonstrated for the first time, without any sample preparation using paper spray mass spectrometry (PS-MS). The presence of Duomeen O in water samples was confirmed via tandem mass spectrometry using collision-induced dissociation and supported by exact mass measurement and reactive paper spray experiments using an LTQ Orbitrap Exactive instrument. Data shown herein indicate that paper spray ambient ionization can be readily used as a rapid and robust method for in situ direct analysis of polymanine corrosion inhibitors in an industrial water boiler plant and other related samples in the water treatment industry. This approach was applied for the analysis of three complex water samples including feedwater, condensate water, and boiler water, all collected from large medium pressure (MP) water tube boiler plants, known to be dosed with varying amounts of polyamine and amine corrosion inhibitor components. Polyamine chemistry is widely used for example in large high pressure (HP) boilers operating in municipal waste and recycling facilities to prevent corrosion of metals. The samples used in this study are from such a facility in Coventry waste treatment facility, U.K., which has 3 × 40 tonne/hour boilers operating at 17.5 bar.

Development of a poly(ethylene glycol)–graphene oxide sol–gel coating for solid-phase microextraction of aromatic amines in water samples with a gas chromatography-flame ionization detector method

The wrinkled structure of a PEG–GO sol–gel coating increases the surface area on the fiber, the speeds of extraction and desorption steps and sample capacity.

Determination of Anilines and Toluidines in Water by Salt-Assisted Dispersive Liquid–Liquid Microextraction Combined with GC-FID

Dispersive liquid–liquid microextraction (DLLME) assisted with salting-out was applied for the determination of five aromatic amines in water samples by using gas chromatography with flame ionization detection. In this extraction method, several factors influencing the extraction efficiency of the target analytes, such as extraction and disperser solvent type and their volume, salt addition and amount, and pH, were studied and optimized. Under the optimal DLLME conditions, good linearity was observed in the range of 4–1,000 ng mL−1 with the RSDs from 1.2 to 7.9 %. The LODs based on S/N of 3 ranged from 0.2 to 3.4 ng mL−1 and the enrichment factors ranged from 207 to 4,315. The proposed method was successfully applied to the water samples collected from the tap and the lake, and the relative recoveries were in the range of 87.7–108.4 %.

Analysis of amines in water samples by high performance liquid chromatography-laser induced fluorescence detection

A sensitive high performance liquid chromatography (HPLC)-laser induced fluorescence detection (LIFD) method was developed for the determination of amines. The derivatization and separation conditions were investigated. Under the optimized conditions, spermidine, putrescine and histamine were analyzed. The limits of detection (LODs) of the three biogenic amines (S/N = 3) were as low as 10(-10) mol/L. This method showed excellent stability. The RSDs of retention times and peak areas of the three biogenic amines were lower than 0.3% and 3%, respectively. This method was applied in biogenic amine analysis in water samples, and the average recoveries were in the range of 94.99%-104.7%. Furthermore, the amines in seven tea samples were analyzed by this method, and satisfactory results were achieved. The developed assay is of excellent sensitivity and good reproducibility, which can be used in the analysis of the amines in water samples.

Optimization of simultaneous derivatization and extraction of aliphatic amines in water samples with dispersive liquid–liquid microextraction followed by HPLC

Dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) with simultaneous derivatization followed by high-performance liquid chromatography-diode array detection (HPLC-DAD) was applied for preconcentration and determination of primary and secondary aliphatic amines in environmental water samples. A ternary mixture consisting of a disperser, an extractant and a derivatization reagent was used for the simultaneous derivatization and extraction of aliphatic amines in different water samples. The effects of various experimental parameters on derivatization and extraction efficiency were studied simultaneously using experimental design. A Plackett-Burman design was performed for screening of variables in order to determine the significant variables affecting the extraction efficiency. Then, the significant factors were optimized by using a Box-Behnken design (BBD) and the response surface equations were derived. Under optimal conditions, the preconcentration factors were between 210 and 290. The limit of detections (LODs) ranged from 0.005 to 0.02 μg/L and dynamic linear ranges (DLRs) of 0.05-500 and 0.1-500 μg/L were obtained for most of analytes. The performance of the method was evaluated for extraction and determination of primary and secondary aliphatic amines in environmental water samples in micrograms per liter and satisfactory results were obtained (RSDs <12.5%).

Optimization of solvent bar microextraction combined with gas chromatography for the analysis of aliphatic amines in water samples

Solvent bar microextraction (SBME) combined with gas chromatography-flame ionization detector (GC-FID), was used for preconcentration and determination of some aliphatic amines in waste water samples. The effect of different variables on the extraction efficiency was studied simultaneously using an experimental design. The variables of interest in the SBME were ionic strength, organic additive effect, sodium hydroxide concentration, stirring rate and extraction time and temperature. A Plackett-Burman design was performed for screening in order to determine the significant variables affecting the extraction efficiency. Then, the significant factors were optimized by a Box-Behnken design (BBD) and the response surface equations were derived. The optimum experimental conditions were sodium chloride concentration, 20% (w/v); sodium hydroxide concentration, 1 mol L(-1); stirring rate, 700 rpm; extraction temperature, 45 degrees C; extraction time, 30 min, and without addition of acetone. Under the optimum conditions, the preconcentration factors were between 260 and 1130. The limit of detections (LODs) ranged from 0.01 microg L(-1) (for dibutylamine) to 0.06 microg L(-1) (for N-ethyldiisopropylamine). The linear dynamic ranges (LDRs) of 0.05-800 and 0.1-600 microg L(-1) were obtained for most of the analytes. The performance of the method was evaluated for extraction and determination of aliphatic amines in waste water samples in the range of microgram per liter and satisfactory results were obtained (RSDs<13.6%).

Comparison of several solid-phase extraction sorbents for continuous determination of amines in water by gas chromatography–mass spectrometry

A semiautomatic method has been proposed for the determination of different types of amines in water samples including anilines, chloroanilines, N-nitrosamines and aliphatic amines. The analytes were retained on a solid-phase extraction sorbent column and after elution, 1μL of the extract was analysed by gas chromatography coupled with electron impact ionization mass spectrometry. A systematic overview is given of the advantages and disadvantages of several sorbents (LiChrolut EN, Oasis HLB, RP-C18, graphitized carbon black, fullerenes and nanotubes) in the retention of amine compounds and based on sensitivity, selectivity and reliability. The retention efficiency for the studied amines was higher (ca. 100%) with LiChrolut EN and Oasis HLB than it was with RP-C18 and fullerenes (53 and 62%, respectively, on average). Detection limits of 0.5–16ngL−1 for the 27 amines studied were obtained when using a sorbent column containing 75mg of LiChrolut EN for 100mL of sample, the RSD being lower than 6.5%. The method was applied with good accuracy and precision in the determination of amines in various types of water including river, pond, tap, well, drinking, swimming pool and waste.

Sensitive determination of strongly polar aromatic amines in water samples by stir bar sorptive extraction based on poly(vinylimidazole-divinylbenzene) monolithic material and liquid chromatographic analysis

A simple and sensitive method for the determination of polar aromatic amines (PAAs) was developed using stir bar sorptive extraction (SBSE) coupling to high-performance liquid chromatography. A hydrophilic poly(vinylimidazole-divinylbenzene) (VIDB) monolithic material was prepared and acted as SBSE coating. The influences of polymerization conditions for VIDB on the extraction efficiency were investigated using aniline and 2,4-dinitroaniline as detected solutes. To achieve optimum extraction performance for PAAs, several parameters including extraction and desorption time, desorption solvent, ionic strength and pH value of sample matrix were investigated. The results showed that under the optimized experimental conditions, the method showed good sensitivity and excellent recoveries, as well as advantages such as linearity, simplicity, low cost and high feasibility. The extraction performance of present method to the target compounds also compared with commercial SBSE which using polydimethylsiloxane as coating and other SBSE which based on monolithic materials. Finally, the proposed method was successfully applied to the determination of PAAs in lake and sea waters, and excellent recoveries of spiked target compounds in real samples were obtained.

Ultrasound-assisted ionic liquid dispersive liquid-phase micro-extraction: A novel approach for the sensitive determination of aromatic amines in water samples

Ultrasound-assisted ionic liquid dispersive liquid-phase micro-extraction was developed for the determination of four aromatic amines such as 2,4-dichloroaniline, 1-naphthylamine, 6-chloroanline and N,N-dimethylaniline. High-performance liquid chromatography coupled with UV detector was used for the determination of aromatic amines. In the novel procedure, 1-hexyl-3-methylimidazolium hexafluorophosphate [C 6MIM] [PF 6] was dispersed into the aqueous sample solution as fine droplets by ultrasonication, and which promoted the analytes more easily migrate into the ionic liquid phase. Variable affecting such as the volume of [C 6MIM] [PF 6], sample pH, ultrasonication time, extraction time, centrifuging time have been investigated in detail. The proposed method has been found to have excellent detection sensitivity with limits of detection (LOD, S/N = 3) in the range of 0.17–0.49 μg L −1 and precisions in the range of 2.0–6.1% (RSDs, n = 6). This method has been also successfully applied to analyze the real water samples and good spiked recoveries over the range of 92.2–119.3% were obtained.

On-line determination of aliphatic amines in water using in-tube solid-phase microextraction-assisted derivatisation in in-valve mode for processing large sample volumes in LC

This paper describes a cost-effective procedure for the analysis of short-chain aliphatic amines in water samples using a solid-phase microextraction device. Analyte preconcentration and derivatisation were effected into a capillary column coated with 95% polydimethylsiloxane-5% polydiphenylsiloxane, which was used as the injection loop of a Rheodyne injection valve. The coating was previously loaded with the derivatisation reagent, 9-fluorenylmethyl chloroformate. A volume of 1 mL of samples was then drawn into the capillary column, and the extracted analytes were left to react on the capillary coating for 5 min. Next, the capillary column was cleaned by passing water. Finally, the injection valve was rotated, and the derivatives formed were dynamically desorbed and transferred to the analytical column into the mobile phase. Methylamine, ethylamine, propylamine, n-butylamine and n-pentylamine were selected as model compounds. Excellent sensitivity was achieved, being the limits of detection of 15-200 microg/L when using UV detection and of 0.1-0.4 microg/L by fluorescence.

Determination of aromatic amines in water samples by capillary electrophoresis with amperometric detection

Aromatic amines such as aniline and its derivatives are an important class of environmental water pollutants. A method based on capillary zone electrophoresis with amperometric detection (CZE-AD) at carbon disk electrode was developed for the determination of aromatic amines in water samples. The effects of working potential, pH and concentration of running buffer, separation voltage and injection time were investigated. Under the optimum conditions, 2,3-diaminonaphthalene, aniline, o-phenylenediamine and p-chloroaniline could be separated in 0.16 mol/L Na(2)HPO(4)-citric acid buffer (pH 4.6) within 23 min. The detection limits of them were 1.0 x 10(-7), 3.3 x 10(-8), 5.0 x 10(-8), and 1.3 x 10(-7)mol/L (S/N=3), respectively. The method can be applied directly for the determination of aromatic amines in real water samples with satisfactory results.

Determination of four aromatic amines in water samples using dispersive liquid–liquid microextraction combined with HPLC

A new method for the determination of four aromatic amines in water samples was developed by using dispersive liquid-liquid microextraction (DLLME) technique combined with HPLC-variable wavelength detection (HPLC-VWD). In this extraction method, 0.50 mL methanol (as dispersive solvent) containing 25.0 microL tetrachloroethane (as extraction solvent) was rapidly injected by a syringe into 5.00 mL water sample. Accordingly, a cloudy solution was formed. After centrifugation for 2 min at 4000 rpm, the fine droplets of the tetrachloroethane containing the analytes were sedimented in the bottom of the conical test tube (7+/-0.2 microL). Then, 5.0 microL of the settled phase was determined by HPLC-VWD. Parameters such as the kind and volume of extraction solvent and dispersive solvent, extraction time, and salt concentration were optimized. Under the optimum conditions, the enrichment factors ranged from 41.3 to 94.5. Linearity was observed in the range of 5-5000 ng/mL. The LODs based on S/N of 3 ranged from 0.8 to 1.8 ng/mL. The RSDs (for 400 ng/mL of p-toluidine and o-chloroaniline, 100 ng/mL of p-chloroaniline and p-bromoaniline) varied from 4.1 to 5.3% (n=6). The water samples collected from rivers and lakes were successfully analyzed by the proposed method and the relative recoveries were in the range of 85.4-111.7% and 90.2-101.3%, respectively.

Ionic liquid based dispersive liquid–liquid microextraction of aromatic amines in water samples

In this work, a new microextraction method termed ionic liquid based dispersive liquid–liquid microextraction (IL-DLLME) was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4-aminobiphenyl in aqueous matrices. After extraction the ionic liquid (IL) phase was injected directly into the high performance liquid chromatography (HPLC) system for determination. Some parameters that might affect the extraction efficiency were optimized. Under the optimum conditions, good linear relationship, sensitivity and reproducibility were obtained. The limits of detection (LOD, S/N = 3) for the four analytes were in the range of 0.45–2.6 μg L −1. The relative standard deviations (R.S.D., n = 6) were in the range of 6.2–9.8%. This method was applied for the analysis of the real water samples. The recoveries ranged from 93.4 to 106.4%. The main advantages of the method are high speed, high recovery, good repeatability and volatile organic solvent-free.

A sweeping‐micellar electrokinetic chromatography method for direct detection of some aromatic amines in water samples

A simple and rapid sweeping method for the online improvement of detection limit of some aromatic amines has been developed in this work. The optimum sweeping and separation conditions for 4-methylaniline, 3,4-dichloroaniline, 4-chloroaniline, and 4-aminophenyl were investigated in detail. Under the optimum conditions, the detection limits of these four aromatic amines ranged from 5.4 x 10(-10) to 4.6 x 10(-8)mol/L (S/N = 3), which was about 80-1090-folds lower than those of conventional sample injections. Linear response range were in the range of 2.5 x 10(-8)-2.0 x 10(-6)mol/L with the correlation coefficient between 0.9965 and 0.9994. Baseline separation was achieved within 10 min. After validation, the developed method was applied to determine 4-methylaniline, 3,4-dichloroaniline, 4-chloroaniline, and 4-aminophenyl in river water sample with average recoveries of 79.6-88.7%.

Sensitive determination of total aliphatic amines in water samples by spectrofluorimetry using the new fluorogenic probe 3-(4-fluorobenzoyl)-2-quinolinecarboxaldehyde

A rapid and highly sensitive fluorogenic method has been developed for the determination of total primary aliphatic amines with a novel fluorogenic derivatizing reagent, 3-(4-fluorobenzoyl)-2-quinolinecarboxaldehyde (FBQCA). FBQCA selectively reacts with amines to form a highly fluorescent isoindole in buffer of pH 9.7 and in the presence of potassium cyanide solution. The fluorescence intensity of derivatized products are detected at λex/λem = 480/546 nm. The results of the experiments showed a linear dynamic range of 1 × 10−8 to 6 × 10−6 mol L−1 with a detection limit (S/N = 3) of 6 nmol L−1. The method was successfully used for the direct spectrofluorimetric determination of aliphatic amines in water samples with recoveries of 95–104%.

Ionic liquid for improved single-drop microextraction of aromatic amines in water samples

A new method was developed for the analysis of 1-naphthylamine, N,N-dimethylaniline and diphenylamine in water samples by improved single-drop microextraction with 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM]PF6). Factors such as salt concentration, sample temperature, stirring rate, extraction time, pH and organic drop volume were systematically investigated. Under the optimized conditions, an excellent linear relationship was achieved in the range of 1.0–100 µg L−1 for 1-naphthylamine, diphenylamine, and 0.5-100 µg L−1 for N,N-dimethylaniline, respectively. The detection limits varied between 0.09–0.38 µg L−1, and enrichment factors ranged from 13.7 to 116.3. The precision of the method was below 8.1% (RSD). It was successfully applied to the determination of these aromatic amines in water samples. The results demonstrated that this procedure represents an efficient and sensitive method for the analysis of aromatic amines in water samples.

Development of gas chromatography–mass spectrometry following headspace single-drop microextraction and simultaneous derivatization for fast determination of short-chain aliphatic amines in water samples

In this work, for the first time, gas chromatography–mass spectrometry (GC–MS) following headspace single-drop microextraction (HS-SDME) and simultaneous derivatization was developed for fast determination of short-chain aliphatic amines (SCAAs) in water samples. In the proposed method, SCAAs in water samples were headspace extracted and concentrated by suspending a microdrop of solvent, and SCAAs extracted in the microdrop of solvent were simultaneously and rapidly reacted with pentafluorobenzaldehyde (PFBAY). The formed SCAA derivatives were analyzed by GC–MS. The HS-SDME parameters of solvent selection, solvent volume, sample temperature, extraction time and stirring rate were studied, and the method linearity, precision and detection limits, were also studied. The results show that the proposed method provided good linearity ( R 2 > 0.99, 5.0–500 ng/ml), low detection limit (0.6–1.1 ng/ml), and good precision (RSD value less than 10%). The proposed method was further tested by its application to quantitative analysis of SCAAs in four wastewater samples. The experiment results have demonstrated that GC–MS following HS-SDME and simultaneous derivatization is a simple, rapid and low-cost method for the determination of SCAAs in water samples.