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.

A novel indicator system for catalytic spectrophotometric determination and speciation of inorganic selenium species (Se(Ⅳ), Se(Ⅵ)) at trace levels in natural lake and river water samples

A novel catalytic kinetic method is proposed for the determination of Se（Ⅳ）, Se（Ⅵ）, and total inorganic selenium in water based on the catalytic effect of Se（Ⅳ） on the reduction of Celestine blue by sodium sulfide at pH 7.0 phosphate buffer. The fixed-time method was adopted for the determination and speciation of inorganic selenium. Under the optimum conditions, the two calibration graphs are linear with a good correlation coefficient in the range 2-20 and 20-200 μg·L-1 of Se（Ⅳ） for the fixed-time method at 30℃. The experimental and theo- retical detection limits of the developed kinetic method were found to be 0.21 and 2.50 μg·L-1 for the fixed-time method （3 min）. All of the variables that affect the sensitivity at 645 nm were investigated, and the optimum conditions were established. The interference effect of various cations and anions on the Se（Ⅳ） determination was also studied. The selectivity of the selenium determination was greatly improved with the use of the strongly cation exchange resin such as Amberlite IR120 plus as long as chelating agents of thiourea and thiosulphate. The proposed kinetic method was validated statistically and through recovery studies in natural water samples. The relative standard deviations （RSDs） for ten replicate measurements of 2, 10, and 20 μg·L-1 of Se（Ⅳ） change between 0.35% and 5.58%, while the RSDs for ten replicate measurements of 3, 6, and 12 μg·L-1 of Se（Ⅵ） change between 0.49% and 1.61%. Analyses of a certified standard reference material （NIST SRM 1643e） for selenium using the fixed-time method showed that the proposed kinetic method has good accuracy. The Se（Ⅳ）, Se（Ⅵ）, and total inorganic selenium in lake and river water samples have been successfully determined by this method after selective reduction of Se（Ⅵ） to Se（Ⅳ）.

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.

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 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%.

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.

Determination of Cobalt in Food, Environmental and Water Samples with Preconcentration by Dispersive Liquid-Liquid Microextraction

A new method for the determination of cobalt was developed by dispersive liquid-liquid microextraction preconcentra-tion and flame atomic absorption spectrometry. In the proposed approach, 1,5-bis(di-2-pyridyl) methylene thiocarbohydrazide (DPTH) was used as a chelating agent, and chloroform and ethanol were selected as extraction and dispersive solvents. Some factors influencing the extraction efficiency of cobalt and its subsequent determination, including extraction and dispersive solvent type and volume, pH of sample solution, concentration of the chelating agent, and extraction time, were studied and optimized. Under the optimum conditions, a preconcentration factor of 8 was reached. The detection limit for cobalt was 12.4 ng?mL–1, and the relative standard deviation (RSD) was 3.42% (n = 7, c = 100 ng?mL–1). The method was successfully applied to the determination of cobalt in food, environmental and water samples.

Rapid Determination of Three Kinds of Microcystins in Environmental Water Samples by Disk SPE-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

A method of rapidly detecting three kinds of microcystins( MCs) in environmental water samples by using disk SPE- ultra high performance liquid chromatography- tandem mass spectrometry( UPLC- MS / MS) was established. Firstly,environmental water samples were extracted by disk SPE column( C_(18)),and three kinds of MCs were separated by Waters BEH C_(18) chromatographic column with acetonitrile- 0. 2% formic acid solution as the mobile phase. After the gradient elution separation,the external standard method was used for quantitative and qualitative analysis under MRM of UPLC- MS / MS. The results showed that the three kinds of MCs in the range of 0. 05- 10 μg / L showed good linear relation,and the correlation coefficients were higher than 0. 999 4,while the method detection limit was 0. 04 ng / L. Under 0. 1,1,and 5 μg / L standard addition for the same environmental sample,the average recovery was 82. 8%- 108. 8%,and the relative standard deviation of determination results was2. 1%- 10. 1%( n = 6). This method is rapid,sensitive and accurate,so it can be effectively applied in the monitoring of MCs in environmental water samples.

The Effect of Measuring Magnetic Susceptibility of Water Samples by Starting with Isothermal Remanent Magnetization (IRM) before Anhysteretic Remanent Magnetization (ARM)

Estimating magnetic properties of water samples by first measuring the Anhysteretic Remanent Magnetization (ARM) before Isothermal Remanent Magnetization (IRM) is induced has been costly due to the discard of samples measured by staring with the latter before the former. However, no clear understanding exists on the effect of measuring magnetic properties values by first inducing IRM before ARM. This study explored the effect of measuring concentration related parameters (χlf, χfd and χARM), a mineral related parameter (S-300) and grain size parameters (χfd% and χARM/SIRM ratio) fromwater samples by starting with IRM before ARM. Forty three surface water samples were collected from the estuarine of Yangtze River (China) with the aim of measuring magnetic characteristics by starting with IRM before ARM. The results indicated that, measuring magnetic properties by either starting with ARM or IRM led to similar values for χlf, χfd, χfd%, χARM, S-300 and χARM/SIRM ratio (p > 0.05). These results imply that, measuring concentrationrelated parameters does not necessarily require measuring ARM first and then IRM. Researchers can start by measuring any parameter between ARM and IRM without affecting the final results of the water samples, but with proper demagnetization when started with IRM.

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.

Developed New Procedure for Low Concentrations of Hydrazine Determination by Spectrophotometry: Hydrazine-Potassium Permanganate System

An indirect, sensitive and accurate method for the determination of trace amounts of hydrazine is described. In this proposed the spectrophotometric method is based on its reduction properties of hydrazine with a known concentration of potassium permanganate to reduce the colour. The absorbance of unreduced permanganate is measured the colour difference at different wavelengths 546 and 526 nm which show an absorption spectrum with hydrazine. Hydrazine can be determined in the range of 100 - 700 μg/ml with correlation coefficient of 0.999 and relative standard deviation 1%. The method is successfully applied for the determination of hydrazine in water streams in nuclear reactors/purex process/boiler water and polluted 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.