A combination of dispersive liquid–liquid microextraction and surface plasmon resonance sensing of gold nanoparticles for the determination of ziram pesticide

We have developed a reliable, fast, and highly sensitive analytical method utilizing dispersive liquid–liquid microextraction and gold nanoparticles probes for ziram (zinc bis(dimethyldithiocarbamate)) determination. The method is based on the in situ formation of gold nanoparticles in carbon tetrachloride as an organic phase. It was found that the trace levels of ziram influenced the formation of gold nanoparticles, leading to absorbance change of a sedimented phase. The results of the colorimetric ziram determination were in the concentration range of 0.12–2.52 ng/mL with a limit of detection of 0.06 ng/mL. The formation of the stable and dispersed gold nanoparticles in the organic phase provides a good precision for dispersive liquid–liquid microextraction method, resulting in the relative standard deviation of 3.8 and 1.2% for 0.56 and 1.58 ng/mL of ziram, respectively. This method has been successfully used for the ziram determination in samples of well and river water, soil, potato, carrot, wheat, and paddy soil.     

Microfunnel‐filter‐based emulsification microextraction followed by gas chromatography for simple determination of organophosphorus pesticides in environmental water samples

A simple and fast method named microfunnel‐filter‐based emulsification microextraction is introduced for an efficient determination of some organophosphorus pesticides including diazinon, malathion, and chlorpyrifos in the environmental samples including the river, sea, and well water. This method is based upon the dispersion of a low‐toxicity organic solvent (dihexyl ether), as the extractant, in a high volume of an aqueous sample solution (45 mL). It is implemented without a centrifugation step, and using a syringe filter and a micro‐funnel, the phase separation and transfer of the enriched analytes to the gas chromatograph are simply achieved. By filtration of the extractant phase, a suitable sample clean‐up is obtained, and the total extraction time is just a few minutes. The factors influencing the extraction efficiency are optimized, and under the optimal conditions, the proposed method provides a good linearity (in the range of 15–1500 ng/mL (R² > 0.996). A high enrichment factor is obtained (in the range of 306–342), and the method provides low limits of detection and quantification (in the ranges of 4–8 and 15–25 ng/mL, respectively).     

Optimization and validation of organochlorine compounds in adipose tissue by SPE‐gas chromatography

Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid‐phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C₁₈‐E), benzenesulfonic acid modified silica cation exchanger (SA), poly(styrene‐divinylbenzene (EN) and EN/RP₁₈ SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC–ECD). The C₁₈‐E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries > 70% with standard deviations (SD) < 15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003–0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC‐MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p′‐DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

A Photochemistry Technique Using Ultraviolet Irradiation Followed by Gas-Liquid Chromatography to Confirm the Identity of Some Organochlorine Pesticides

Abstract

A procedure involving ultraviolet (UV) irradiation followed by gas-liquid chromatographic (GLC) detection of photodecomposition products to confirm the identity of selected organochlorine pesticides is described. The Irradiation intensity was standardized by determining the position relative to the UV source which resulted in equal GLC peak heights for the parent compound and major photo-decomposition product after 8 minutes of exposure of a solution of heptachlor epoxide in isooctane. Chromatograms showing photo-decomposition patterns for 33 compounds are presented. Observations and comments on the applicability of this technique to organo-chlorine pesticide residue confirmation are reported.     

Multiresidue Method for the Determination of Organophosphorus Pesticides in Still Wine and Fortified Wine Using Solid-Phase Microextraction and Gas Chromatography – Tandem Mass Spectrometry

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1–14.3 µg/L and 0.2–43.3 µg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R²) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed.     

Trace Metal and Persistent Organochlorine Levels in Wood Bison (Bison bison athabascae) from the Mackenzie Bison Sanctuary

Abstract

Tissue samples were collected from ten healthy mature female wood bison (B. bison athabascae) for examination. Livers and kidneys were tested for toxic heavy metals and trace metals considered as essential nutrients for successful reproduction, while fat samples were analyzed for persistent chlorinated hydrocarbons. No elevated levels of toxic heavy metals (arsenic, cadmium, lead, mercury) were found and essential trace elements (copper, manganese, selenium, zinc) were within the acceptable ranges established for healthy cattle. All fat samples tested contained trace levels of α-BHC (mean value, 23 ppb) and lindane (mean value, 3 ppb).     

Electrochemical Determination of Fenitrothion Organophosphorus Pesticide Using Polyzincon Modified‐glassy Carbon Electrode

In this paper, a glassy carbon electrode (GCE) was modified with polyzincon. The modified electrode was used as a simple, inexpensive and highly sensitive electrochemical sensor for the determination of organophosphorus pesticide fenitrothion. To fabricate the electrochemical sensor, GCE was immersed in 0.10 mmol L⁻¹ zincon solutions at pH 7.0 and then successively scanned between −1.00 to 2.20 V (vs . Ag/AgCl) at a scan rate of 70 mV s⁻¹ for six cycles. The morphology and structure of the polyzincon were studied with atomic force microscopy and scanning electron microscopy. A comparison of the electrochemical behavior of fenitrothion on the unmodified and polyzincon modified‐GCE showed that in the modified electrode not only the oxidation peak current increased, but also the overpotential shifted to lower one. The experimental conditions such as sample solution pH, accumulation potential, and time were optimized. The differential pulse voltammetric responses of fenitrothion at potential about −0.60 V was used for the determination of fenitrothion. The peak current increased with increasing the concentration of fenitrothion in the range of 5 to 8600 nmol L⁻¹ with a detection limit of 1.5 nmol L⁻¹. Finally, the electrochemical sensor was used for the analysis of fenitrothion in water and fruit samples.     

Low‐density extraction solvent based solvent‐terminated dispersive liquid–liquid microextraction for quantitative determination of ionizable pesticides in environmental waters

A rapid, efficient, and new solvent terminated dispersive liquid–liquid microextraction technique coupled with HPLC was developed for selective extraction and analysis of s‐triazine herbicides from environmental water samples. Important parameters influencing the extraction process including type and volume of extraction and disperser solvent, extraction time, sample pH, ionic strength, and extraction temperature were successfully optimized. Under the optimal conditions, there are excellent linear relationships between the analytical results and concentration in the range of 10–400 mg/L for atrazine, propazine, prometryn, and terbutryn. LOD and LOQ ranged from 0.60 to 2.33 μg/L and 2.0 to 7.7 μg/L, respectively. Performance of the analytical technique was evaluated by carrying out the repeatability and reproducibility analyses that were ranged from 2.86 to 5.66% and 4.64 to 5.89% for 100 μg/L of each target analyte, respectively. The proposed method has been successfully applied to the analysis of real water samples and acceptable relative recoveries over the range of 65.93–101.46%, with RSDs ≤ 8.80%, were obtained. The overall results have been compared with the literature values. Thus, the method developed could efficiently be used for selective extraction of the target analytes from complex matrices, particularly environmental waters.     

Graphene grafted silica‐coated Fe3O4 nanocomposite as absorbent for enrichment of carbamates from cucumbers and pears prior to HPLC

In this paper, a novel graphene (G) grafted silica‐coated Fe₃O₄ nanocomposite was fabricated by the chemical bonding of G onto the surface of silica‐coated Fe₃O₄ nanoparticles. Some carbamates (metolcarb, carbaryl, pirimicarb, and diethofencarb) in cucumber and pear samples were enriched by this nanocomposite prior to their determination by HPLC with UV detection. Experimental parameters that may affect the extraction efficiency were investigated. Under the optimum conditions, a linear response was achieved in the concentration range of 0.5–100.0 ng/g for metolcarb, carbaryl, and diethofencarb, and 1.0–100 ng/g for pirimicarb with the correlation coefficients (r) ranging from 0.9956 to 0.9984. The LOD (S/N = 3) of the method were found to be in the range from 0.08 to 0.2 ng/g. The RSDs were in the range from 2.4 to 5.8%. The results indicated that the G grafted silica‐coated Fe₃O₄ nanocomposite was stable and efficient for magnetic SPE and has a great application potential for the preconcentration of other organic pollutants from real samples.     

Determination of Anionic Surfactants in Water

The use of ternary complexes in the determination of anionic surfactants has been investigated and an analytical method using linear alkyl sulfonates as a test substance has been developed. The method involves the formation of the chloroform-extractable bisphenanthroline Cu(II)-linear alkyl sulfonate (LAS) complex and the subsequent equilibration of the extract with erythrosine to form the extractable bisphenanthroline Cu(II)-erythrosine complex. In the equilibration step erythrosine displaces LAS quantitatively, allowing the determination of the LAS originally present by measuring the absorbance of the extracted bisphenanthroline-Cu(II)-erythrosine complex. Results are reported of studies made to determine the optimum analytical conditions, the sensitivity, and the precision for the method described.