Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

A novel method for the determination of five carbamate pesticides （metolcarb, carbofuran, carbaryl, isoprocard and diethofencard） in water samples was developed by dispersive liquid-liquid microextraction （DLLME） coupled with high performance liquid chromatography-diode array detector （HPLC-DAD）. Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results. Under the optimum conditions for the method, the calibration curve was linear in the concentration range from 5 to 1000 ng mL^-1 for all the five carbamate pesticides, with the correlation coefficients （r^2） varying from 0.9984 to 0.9994. Good enrichment factors were achieved ranging from 80 to 177- fold, depending on the compound. The limits of detection （LODs） （S/N = 3） were ranged from 0.1 to 0.5 ng mL^-1. The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

Application of Modified Silica Coated Magnetite Nanoparticles for Removal of Iodine from Water Samples

The adsorption of iodine onto silica coated magnetite nanoparticles(im-SCMNPs) that modified with imidazole was investigated for removal of high concentrations of iodine from wastewater. Modified silica magnetite nanoparticles showed high efficiency in removing iodine from wastewater samples. The optimum pH for iodine removal was 7.0-8.0. The adsorption capacity was evaluated using both the Langmuir and Freundlich adsorption isotherm models. The size of the produced magnetite nanoparticles was determined by X-ray diffraction analysis and scanning electron microscopy. Synthesized magnetite nanoparticles showed the high adsorption capacity and would be a good method to increase adsorption efficiency for the removal of iodine in a wastewater treatment process. The Langmuir adsorption capacity(qmax) was found to be 140.84 mg/g of the adsorbent.

Determination of triazine herbicide residues in water samples by on-line sweeping concentration in micellar electrokinetic chromatography

A new method for the determination of atrazine, simazine and prometryn in water samples by on-line sweeping concentration technique in micellar electrokinetic chromatography （MEKC） was developed. Various parameters affecting sample enrichment and separation efficiency were systematically studied. Compared with the conventional MEKC method, up to 60-200-fold improvement in concentration sensitivity was achieved in terms of peak height by using this sweeping injection technique. The compound strychnine was used as the internal standard for the improvement of the experimental reproducibility. The limits of detection （S/ N = 3：1） for atrazine, simazine and prometryn were 9, 10 and 0.5 ng mL-1, respectively. This method has been successfully applied to the analysis of atrazine, simazine and prometryn in lake, steam and ground water.

Cloud-point extraction and preconcentration of bisphenol A from water samples

A novel cloud-point extraction （CPE） was successfully used in preconcentration of biphenol A （BPA） from aqueous solutions. Majority of BPA is extracted into the surfactant-rich phase. The parameters affecting the CPE such as concentration of surfactant and electrolyte, equilibration temperature and time and pH of sample solution were investigated. The samples were analyzed by high-performance liquid chromatography with ultraviolet detection. Under the optimized conditions, preconcentration of 10 mL sample gives a preconcentration factor of 11. The limit of detection （LOD） and limit of quantification （LOQ） are 0.1 μg/L and 0.33 μg/L, respectively. The linear range of the proposed method is 0.2-20 μg/L with correlation coefficients greater than 0.998 7 and the spiking recove6es are 97.96%-100.42%. The interference factor was tested and the extraction mechanism was also investigated. Thus, the developed CPE has proven to be an efficient, green, rapid and inexpensive approach for extraction and preconcentration of BPA from water samples.

Rapid determination of atrazine in environmental water samples by a novel liquid phase microextraction

A novel method was described for the rapid determination of atrazine using dispersive liquid phase microextraction in combination with high performance liquid chromatography （HPLC）. Possible impact parameters such as sample pH, extraction and disperser solvents, salting-out effect, and extraction time were investigated. The experimental results indicated that proposed method possessed an excellent analytical performance, The linear range, detection limit, and precision （R.S.D.） were 0.1- 50 ng mL- 1 （R2 = 0.9955）, 0.601 ng mL- 1 and 6,4%, respectively. The proposed method was validated with the real water samples, and the spiked recoveries were in the range of 69.9-89.8%, respectively. These results indicated that the established method with high enrichment factor, short extraction time was an excellent alternative for the routine analysis of atrazine in environmental samples. 2007 Qing Xiang Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Scanning electron microscopy coupled with energydispersive X-ray spectrometry for quick detection of sulfuroxidizing bacteria in environmental water samples

Detection of sulfur-oxidizing bacteria has largely been dependent on targeted gene sequencing technology or traditional cell cultivation, which usually takes from days to months to carry out. This clearly does not meet the requirements of analysis for time-sensitive samples and/or complicated environmental samples. Since energy-dispersive X-ray spectrometry(EDS) can be used to simultaneously detect multiple elements in a sample, including sulfur, with minimal sample treatment, this technology was applied to detect sulfur-oxidizing bacteria using their high sulfur content within the cell. This article describes the application of scanning electron microscopy imaging coupled with EDS mapping for quick detection of sulfur oxidizers in contaminated environmental water samples, with minimal sample handling. Scanning electron microscopy imaging revealed the existence of dense granules within the bacterial cells, while EDS identified large amounts of sulfur within them. EDS mapping localized the sulfur to these granules. Subsequent 16S rRNA gene sequencing showed that the bacteria detected in our samples belonged to the genus Chromatium, which are sulfur oxidizers. Thus, EDS mapping made it possible to identify sulfur oxidizers in environmental samples based on localized sulfur within their cells, within a short time(within 24 h of sampling). This technique has wide ranging applications for detection of sulfur bacteria in environmental water samples.

DETERMINATION OF ANTIMONY IN WATER SAMPLES BY FLOW-INJECTION HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY WITH ON-LINE ION-EXCHANGE COLUMN PRECONCENTRATION

On-line ion-exchange separation and preconcentration were combined with flow-injection hydride generation atomic absorption spectrometry (HGAAS) to determine ultra-trace amounts of antimony in water samples. Antimony(Ⅲ) was preconcentrated on a micro-column packed with CPG-8Q chelating ion-exchanger using time-based sample loading and eluted by 4 mol l^(-1) HCl directly into the hydride generation AAS system. A detection limit (3σ) of 0.0015μg l^(-1) Sb(Ⅲ) was obtained on the basis of a 20 fold enrichment and with a sampling frequency of 60h^(-1). The precision was 1.0% r.s.d.(n=11) at the 0.5μg l^(-1) Sb(Ⅲ) level. Recoveries for the analysis of antimony in tap water, snow water and sea water samples were in the range 97-102%.

Effects of Conservation Methods of Water Samples on Determination of Total Phosphorus

Effects of conservation methods of water samples on determination of total phosphorus were analyzed from aspects of methods of adding conserving agent, SS concentration, natural sedimentation time, conservation temperature and time. The results showed that SS concentration in water and natural sedimentation time had the greatest impact on the determination of total phosphorus, while the influence of methods of adding conserving agent, conservation temperature and time was relatively smaller. TP concentration in water samples conserved irregularly was higher than the standard value due to the existence of SS and microorganisms in water, and the deviation became larger with the increase of SS concentration in water. In addition, quality control measures and matters needing attention during the conservation process of water samples were put forward to improve the accuracy of TP concentration.

Determination of Organochlorine and Synthetic Pyrethroid Pesticide Residues in Water Samples Collected from Different Locations of Bangladesh

The present study was aimed to validate an analytical method for the quantification of 19 organochlorine and 2 synthetic pyrethroid pesticide residues in water samples using modified quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction and Gas Chromatography coupled with Electron Capture Detector (ECD). The selected pesticide residues were determined by in-house validated method. The analytical method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD) and limit of quantification (LOQ). The average recoveries of the selected pesticides ranged from 78% to 117% with RSDr ≤ 12% in two fortification levels of 0.02 and 0.1 mg/L. The linearity was ≥0.995 for all of the selected pesticides. The LOD ranged from 0.003 to 0.006 mg/L and the LOQ was 0.02 mg/L for all the selected analytes. This method was applied satisfactorily for the residue analysis of 108 water samples collected from nine districts of Bangladesh. Among the analyzed samples, only 4 had cypermethrin residues (0.026 mg/L, 0.034 mg/L, 0.045 mg/L and 0.05 mg/L). The level of detected cypermethrin residues were above the WHO recommended guide line values of water quality.

Carbon Dots as“On–Off–On”Fluorescence Sensors for Selective and Consecutive Detection of 4-Nitrophenol and Cerium(IV)in Water Samples

An“on–off–on”fluorescence sensor was designed for rapidly and consecutively detecting 4-nitrophenol and cerium(IV)without the use of any labeling materials.The yellow carbon dots were synthesized by a simple one-step hydrothermal approach,and various techniques were applied to investigate the morphology,structure,and optical properties of the carbon dots.Under the optimal experimental conditions,4-nitrophenol rapidly quenched the fluorescence of carbon dots as a result of the inner filter eff ect(IFE).The fluorescence intensity of carbon dots was linear with the concentration of 4-nitrophenol(1–150μmol/L)and the limit of detection was 0.32μmol/L.The fluorescence was gradually recovered as the cerium(IV)concentration(0.5–100μmol/L)increased in CDs/4-NP,and the limit of detection was 0.16μmol/L.The sensor showed good selectivity and demonstrated high accuracy for the analysis of 4-nitrophenol and cerium(IV)in actual water samples.

Fast Response Fluorescent Probe with a Large Stokes Shift for Thiophenol Detection in Water Samples and Cell Imaging

Herein,the 2,4-dinitrophenyl functional group acting as the thiophenol reactive site was introduced into a carbazole-chalcone fluorophore to synthesize probe-CCF2,which could result in a remarkable increase in fluorescence when reacting with thiophenols.The selectivity and accuracy of probe-CCF2 were investigated with thiophenols,hydrosulphide salt,aliphatic thiols,glutathione,cysteine,anions and metal cations.Probe-CCF2 exhibited a detection limit of 37 nmol/L(R^(2)=0.9951),a remarkable Stokes shift of approximately 130 nm,and a brief response time of 9 min with a remarkable increase in fluorescence of 90-fold.Probe-CCF2 was applied for thiophenol detection in water samples and imaging in living cells successfully,with high sensitivity and excellent selectivity.

Fluorometric determination of nonylphenol in water samples enriched with zirconium doped titanium dioxide nanotubes solid phase extraction

This paper developed a fluorometric method for the sensitive determination of nonylphenol in water samples by preconcentration with zirconium doped titanium dioxide nanotubes solid phase extraction.The parameters on extraction that would influence the enrichment performance such as the kind and volume of eluent,sample pH,sample flow rate,and sample volume were optimized in detail.Under the optimal conditions,the proposed method provided an excellent linear range of 1-150 mg/L and good LOD of 0.076 mg/L.The relative standard deviation（RSD,n = 6） was 2.8%.Proposed method was also used for the analysis of real water samples and the spiked recoveries were satisfied in the range of 98.7-103%.

Preconcentration of chlorophenols in water samples using threedimensional graphene-based magnetic nanocomposite as absorbent

In this paper, a novel magnetic solid-phase extraction method using three-dimensional graphene-based magnetic nanocomposite as adsorbent for the preconcentration of several chlorophenols from water samples prior to high-performance liquid chromatography analysis was developed. Various experimental parameters were investigated. Under the optimum conditions, the enrichment factors of the method were in the range of 186–312, and the limit of detection（S/N = 3） was 0.10 ng/mL. The recoveries of the method were in the range between 85.1% and 101.2%. The developed method has been successfully applied to the determination of chlorophenols in environmental water samples.

A Two-Dimensional NiMoO_(4)Nanowire Electrode for the Sensitive Determination of Hydroquinone in Four Types of Actual Water Samples

Hydroquinone(HQ)poses immeasurable risk to human health and the natural environment on the grounds of high toxicity of organic phenolic compounds.Herein,an innovative electrochemical sensor based on two-dimensional nickel molybdate nanowires(NiMoO_(4)NWs)is constructed for the ultra-sensitive determination of HQ,which can provide useful reference for the human health and environment protection.Two-dimensional NiMoO_(4)NWs are prepared successfully through a facile hydrothermal reaction and annealing process.The obtained two-dimensional NiMoO_(4)NWs are characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),high-resolution TEM(HRTEM),energy-dispersive X-ray spectroscopy(EDS)mapping and X-ray photoelectron spectroscopy(XPS).The accurate contents of Ni and Mo have been characterized by inductively coupled plasma atomic emission spectroscopy(ICP-AES),confirming that the lower content of the nickel in NiMoO_(4)NWs possesses the higher catalytic activity of HQ.Under the optimized conditions,the constructed HQ sensor exhibits satisfactory electrocatalytic activity with a low detection limit of 0.0355μmol/L(S/N=3),a wide linear range of 0.05-4600μmol/L and sensitivity of 170.064μA/(mmol cm^(2)).The sensor has been successfully applied to the detection of HQ in rainwater,tap water,domestic sewage and drinking water samples with satisfactory recovery.At the same time,this sensor has excellent reproducibility,selectivity,and stability.The constructed sensor has potential practical application value and broad application prospect in human health and environmental monitoring.

Comparison of concentration methods for detection of hepatitis A virus in water samples

Hepatitis A virus is a pathogen associated with water pollution.Contaminated drinking water can cause hepatitis A outbreaks,lead to economic losses,and even threaten human lives.It is difficult to detect low levels of hepatitis A virus in water,so the virus must be concentrated in order to quantify it accurately.Here,we present a simple,rapid,efficient technique for the concentration and detection of hepatitis A virus in water.Our data showed that adding phosphate-buffered saline to the water,pre-filtering the water,and adding Trizol reagent directly to the filtration membrane can significantly improve concentration efficiency.Of three types of filtration membranes studied(mixed cellulose ester membrane,polyvinylidene fluoride membrane,and nylon membrane),the concentration efficiency using mixed cellulose ester membrane with a 0.1-μm pore size was the highest,reaching 92.62 ± 5.17%.This method was used to concentrate hepatitis A virus in water samples from Donghu Lake.Using SYBR Green real-time reverse transcription polymerase chain reaction analysis,the detection sensitivity of this method reached 10~1 copies/μL and its concentration efficiency reached 79.45 ± 9.88%.

Determination of Triazine Herbicides in Environmental Water Samples by Acetonitrile Inorganic Salt Aqueous Two-Phase Microextraction System

Acetonitrile inorganic salt aqueous two-phase extraction method was established for the determination of triazine herbicides(simeton,cyanazine,desmetryn,terbumeton,terbuthylazine and dimethametryn)in environmental water samples by high-performance liquid chromatography(HPLC).The extraction solvents types and volume of acetonitrile,the inorganic salt types and amount of(NH_(4))_(2)SO_(4),extraction time and pH of sample solution were optimized by single-factor experiment and central composite design.Under the optimum extraction conditions,all linear ranges were obtained with coefficients of determination(r)≥0.9993.The limits of detection for this proposed method were in the range of 0.16-0.28μg/L for six triazine herbicides.The developed method has been successfully applied to the analysis of target triazine herbicides from lake,canal and moat in real-world water samples.The recoveries of target analytes were in the range from 87.0 to 110.9%and the relative standard deviation was lower than 7.3%.

Determination of Chromium and Nickel in Water Samples by Zinc Oxide Nanoparticle-Chitosan:Equilibrium,Kinetic and Thermodynamic Studies

This study describes the preparation of zinc oxide nanoparticle-chitosan as a solid-phase adsorbent for separation and preconcentration of trace amount of chromium and nickel from environmental water samples and their determination by inductively coupled plasma optical emission spectrometry.Important factors including pH,amount of adsorbent,amount of 1-(2-pyridylazo)-2-naphthol,sample volume,eluent concentration and extraction time were investigated and optimized.The equilibrium data according to the Freundlich’s and Langmuir models were processed.The results showed that the equi-librium data were well fitted with Langmuir isotherm model.The best fit of adsorption kinetics was attained with a second-order equation.Under the optimum conditions,the detection limits for chromium and nickel were 0.041 and 0.039μg L^(−1),respectively,and the relative standard deviations(RSD%)were 1.5%and 1.3%(n=10,c=50μg L^(−1))for chromium and nickel,respectively.This procedure was then used for preconcentration and determination of target compounds from envi-ronmental water samples.

Development of an Indirect Competitive ELISA Based on Polyclonal Antibody for the Detection of Diethylstilbestrol in Water Samples

An indirect competitive enzyme-linked immunosorbent assay （icELISA） based on polyclonal antibody for the estrogen diethylstilbestrol （DES） was developed. With this aim, two different haptens mono-O-3-carboxypropyldiethylstilbestrol （DES-CP） and mono-O-carboxymethyldiethylstilbestrol （DES-CM） with carboxylic group that preserve the molecular structure character of diethylstilbestrol were synthesized. The haptens were conjugated with the carder proteins bovine serum albumin （BSA） by mixed-anhydride method for immunogen and conjugated with ovalbumin （OVA） by active ester method for coating antigen. Polyclonal antibodies for diethylstilbestrol were raised by immunizing mice with immune antigen DES-CP-BSA. Under optimized system, the lowest limit of detection （LLD） of diethylstilbestrol was 0.01 ng/mL, and IC50= 1.02 ng/mL. Its analogs were tested and no obvious cross-reactivity was found to anti-diethylstilbestrol antibody. DES-fortified water samples were determined by simple dilution to diminish the matrix effect. The comparison between the amount of DES estimated by ELISA and the amount added indicates good agreement for all water samples tested, with mean recovery values ranging from 86% to 120.2%.

Determination of aniline derivatives in water samples after preconcentration with oxidized multiwalled carbon nanotubes as solid-phase extraction disk

A sensitive and selective preconcentration method using solid-phase extraction （SPE） disk made from oxidized multiwalled carbon nanotubes （OMWCNTs）, has been developed for the determination of aniline derivatives, such as 2-nitroaniline （2-NA）, 4- nitroaniline （4-NA）, and 2,4-dichloroaniline （2,4-DCA） in water samples. Anilines were extracted onto OMWCNT disk and then determined by high performance liquid chromatography （HPLC） with UV detector. Several parameters on the recovery of the analytes were investigated. The experimental results showed that it was possible to obtain quantitative analysis when the solution pH was 8 using 200 mL of validation solution containing 2 ug of anilines and 10 mL of acetonitrile/ethanol （8/2, v/v） as an eluent. Relative standard deviations for five determinations were 7.5% （2-NA）, 6.5% （4-NA） and 3.8% （2,4-DCA） under optimum conditions. The linear range of calibration curves were 0.5 ng.mL 1 to 15 ng.mL-1 for each analyte with good correlation coefficients. The detection limits （3S/N） of 2-NA, 4-NA and 31 pg.mL -1 and 26 pg.mL-1 was successfully applied to 2,4-DCA were 30pg.mL -1, respectively. Our method the determination of aniline compounds in fiver water sample with high precision and accuracy.