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.

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.

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.

Impact of Water Quality Sampling Process on Environmental Monitoring Results

The sampling of environmental water should ensure the representativeness and integrity of the sampled water body,which has an important impact on the monitoring results.The sampling of different water bodies sampling will result in different monitoring results.Based on the study on the problems and influencing factors in the sampling process of environmental water quality,improvement measures during the sampling process were elaborated in the paper,with the aim to strengthen on-site control of water sampling,and reduce adverse effects on monitoring results.

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.

Long-term changes of phytoplankton community in Xiagu waters of Xiamen,China

Long-term changes of phytoplankton community by water sampling method in Xiagu Sea waters of Xiamen,China,were investigated in this study.Species composition of the phytoplankton community in these waters changed greatly since the 1950s.The numbers of Dinophyta species increased significantly,although Bacillariophyta species are generally dominant.The succession of dominant species in phytoplankton community is obvious： large-size dominant species such as Biddulphia sinensis of the 1950s were gradually replaced by small-size ones such as Cyclotella striata and Nitzschia closterium,and species that still maintain dominant such as Skeletonema costatum are also small ones,leading the whole phytoplankton community of smaller size.Cell density of phytoplankton community increased greatly,among which cell density of the most dominant species Skeletonema costatum have been increasing in exponent function.Margalef index of phytoplankton community decreased,indicating decline of biodiversity of the community,and dominant character of Skeletonema costatum increased.Generally,the structure of the entire phytoplankton community is becoming more and more singular and unstable,which makes the occurrence of red tides more frequent.The succession in the phytoplankton community is related to the long-term changes in marine environment,influenced by human activities and global climate changes,especially the increases of nutrient content.

Development of a competitive format sorbent assay for the determination of parathion in water using molecular imprinted polymer as specific sorbent carrier

A rapid,simple,and reliable competitive molecular imprinted polymer sorbent assay（MIPSA） was developed and validated for measurement of parathion in water samples.This assay employed a molecular imprinted polymer（MIP） that was synthesized with non-covalent imprinting method as capture reagent and p-aminoparathion conjugate of horseradish peroxidase（para-HRP） as an enzyme label.The assay depended on a competitive binding reaction between the enzyme conjugate and analyte for the binding sites of the MIP.The optimized analysis conditions of 10 ng mL-1 para-HRP and 10 mg mL-1 polymer were found.The assay was acceptable to detect parathion in water samples under the optimized conditions,with a limit of detection of 50 ng mL-1.Mean analytical recoveries of added parathion in water samples ranged from 101.2%to 105%.The precision of the assay was satisfactory; relative standard deviation ranged from 4.3%to 6%.

Exploration of Nonlinear Modeling Techniques to Predict the Retention Time of Organic Pollutants in Natural Water and Wastewater

Water pollution affects plants and organisms living in these bodies of water; and, in almost all cases the effect is damaging not only to individual species and populations, but also to the natural biological communities. Genetic algorithm and kernel partial least square （GA-KPLS） and Levenberg- Marquardt artificial neural network （L-M ANN） techniques were used to investigate the correlation between retention time （tR） and descriptors for 150 organic contaminants in natural water and wastewater, which are obtained by gas chromatography coupled to high-resolution time-of-flight mass spectrometry （GC-TOF MS）. The L-M ANN model gave a significantly better performance than the GA-KPLS model. This indicates that L-M ANN can be used as an alternative modeling toot for quantitative structure-retention relationship （QSRR） studies.

Detection of <i>Legionellae pneumophila</i>in Waters by Culture and Polymerase Chain Reaction

Legionella pneumophila (L. pneumophila) is the most common causative agents for all outbreaks of Legionnaires’ disease. Prevention and control of Legionellosis requires surveying and monitoring of Legionella in the environment using conventional and modern technologies. The present study aims to compare detection of L. pneumophila in water samples using both culture and PCR techniques. A pre-enriched contaminated water sample was split into 13 subsamples. Culture and PCR tests were done from the subsamples after different intervals. The results showed a positive PCR result for L. pneumophila after 8 h of incubation. Also, L. pneumophila was detected by culture on non-selective BCYNE agar and selective GPVC agar after 5 and 6 days of incubation respectively. There was no significant difference between the non-selective BCYE- and the selective GVPC method. The PCR procedure was found more sensitive and differed significantly from the conventional selective GVPC method in isolation of L. pneumophila from water samples. It was concluded that pre-enrichment incubation allows the detection of L. pneumophila by PCR within a maximum of 12 h from the collection of 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.

Measuring^(222)Rn in aquatic environment via Pulsed Ionization Chamber Radon Detector

Radon(Rn)is a naturally occurring radioactive inert gas in nature,and^(222)Rn has been routinely used as a powerful tracer in various aquatic environmental research on timescales of hours to days,such as submarine groundwater discharge.Here we developed a new approach to measure^(222)Rn in discrete water samples with a wide range of^(222)Rn concentrations using a Pulsed Ionization Chamber(PIC)Radon Detector.The sensitivity of the new PIC system is evaluated at 6.06 counts per minute for 1 Bq/L when a 500 mL water sample volume is used.A robust logarithmic correlation between sample volumes,ranging from 250 mL to 5000 mL,and system sensitivity obtained in this study strongly suggests that this approach is suitable for measuring radon concentration levels in various natural waters.Compared to the currently available methods for measuring radon in grab samples,the PIC system is cheaper,easier to operate and does not require extra accessories(e.g.,drying tubes etc.)to maintain stable measurements throughout the counting procedure.

水样中三甲基氯化锡的GC-MS测定方法研究

A method of determination of trimethyltin chloride in water samples by GC-MS was developed.Trimethyltin chloride was extracted from water sample by ethyl acetate and detected by GC-MS.The linear range of trimethyltin chloride was from 0.49 to 98.0 μg/mL,r= 0.999 7 and the lowest detection concentration was 0.005 mg/L when the sample volume was 50 mL.The RSD was 4.7%(n=6) and the recovery were 109.4%-117.4%.

Formation of multiple trimethylsilyl derivatives in the derivatization of 17α-ethinylestradiol with BSTFA or MSTFA followed by gas chromatography-mass spectrometry determination

N,O-bis（trimethylsily）trifluoroacetamide （BSTFA） and N-methyl-N（trimethylsily） trifluoroacetamide （MSTFA） are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone （El） and 17α-ethinylestradiol （EE2）. In this study, three trimethylsilyl （TMS） steroid derivatives, mono- and di-trimethylsilyl EE2 and mono-trimethylsilyl El, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz （TMSI） in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.

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%.

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%.