The speciation of inorganic arsenic in soil and vegetables irrigated with treated municipal wastewater.

In this research, an environmental friendly, green and efficient sample preparation method using vortex-assisted microextraction based on a deep eutectic solvent (VAME-DES) followed by graphite furnace atomic absorption spectrometry (GFAAS) was developed for the preconcentration and determination of As(iii)/As(v) and total inorganic arsenic in soil and vegetables irrigated with treated municipal wastewater from Tehran and Kermanshah, Iran. In the proposed method, a novel DES, characterized by its low density, was prepared by mixing choline chloride and citric acid monohydrate at a molar ratio of 1 : 1. Under optimal conditions, the proposed method enabled the achievement of a good enrichment factor of 175. The calibration graph was linear in the range of 0.3-100 µg kg-1 and the limit of detection (LOD) was 0.10 µg kg-1. The repeatability and reproducibility of the method based on seven replicate measurements of 50 µg kg-1 As(iii) in analysed samples were 4.2% and 6.5, respectively. The relative recoveries from soil and vegetables that were spiked with different levels of As(iii) and As(v) were 94.2-104.3 and 91.0-107.0%, respectively. The main advantage of the proposed method is the use of a non-toxic and non-volatile DES instead of volatile organic solvents. The accuracy of the proposed procedure was also assessed by the speciation of arsenic in two standard reference materials (GBW10014 cabbage and GBW10015 spinach). The extraction methodology is simple, rapid, cheap and green, since only small amounts of non-toxic solvents are necessary.

Homogeneous liquid-liquid microextraction based on liquid nitrogen-induced phase separation followed by GFAAS for sensitive extraction and determination of lead in lead-adulterated opium and refined opium.

Herein, we developed a novel homogeneous liquid-liquid microextraction based on liquid nitrogen-induced phase separation (HLLME-LNPS) for the extraction and determination of lead (Pb) in Pb-adulterated opium and refined opium by GFAAS analysis. In this procedure, first, 400 µl of acetonitrile (extractant) containing 7.0 µl of diethyl dithiophosphoric acid (DDTP) is injected into a sample solution and a homogeneous solution is formed. Subsequently, the homogeneous mixture is cooled using liquid nitrogen for 16 seconds. By this process, due to the difference in the freezing points of the organic and aqueous phases, the homogeneous state is broken and the Pb-DDTP species are extracted into the liquid organic phase collected on top of the frozen aqueous phase. The introduced method exhibited a good linearity with a coefficient of determination (r 2) of 0.9988 and an acceptable linear range of 0.6-100 µg l-1. Accordingly, the detection limit was 0.2 µg l-1 (S/N = 3) for Pb ions, and a high enrichment factor was obtained. The proposed method was successfully utilized to determine trace levels of Pb in opium samples. The results of the sample analysis showed that 65% of the opium samples and 85% of the refined opium samples had much higher than expected levels of contaminating Pb, and this contamination poses a serious threat to drug users.

Optimization of a new methodology for trace determination of elements in biological fluids: Application for speciation of inorganic selenium in children's blood.

The continuous sample drop flow microextraction (CSDFME) joined with the iridium-modified tube graphite furnace atomic absorption spectrometry (GFAAS) has been developed as a highly sensitive technique for the speciation of selenium in blood samples. In this method 32.0µl carbon tetrachloride is transferred to the bottom of a conical sample cup. Then the 5.0ml of aqueous solution transforms to fine droplets while passing through the organic solvent. At this stage, Se(IV)-APDC hydrophobic complex is extracted into the organic solvent. After extraction, the conical sample cup is transferred to the GFAAS and 20µl of extraction solvent was injected into the graphite tube by the aim of autosampler. Under the optimum conditions, the calibration graph was linear in the range of 0.06-3.0µgl-1 with detection limit of 0.02µgl-1. The enrichment factor and enhancement factor were 106 and 91, respectively. Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 2.5µgl-1 of selenium were 3.7% and 4.2%, respectively. Total inorganic Se(IV, VΙ) was measured after reduction of Se(VΙ) with gentle boiling in 5M HCl medium for 50min and adjusting pH to 3, and the concentration of Se(VΙ) was calculated by subtracting the Se(IV) concentration from the total selenium concentration.

Speciation of inorganic arsenic species and total inorganic arsenic in rice using microwave-assisted dispersive liquid-liquid micro-extraction and electrothermal atomic absorption spectrometry.

Human exposure to inorganic arsenic (iAs) via rice consumption is of increasing concern. In the present study, microwave-assisted dispersive liquid-liquid micro-extraction (MADLLME) and electrothermal atomic absorption spectrometry (ETAAS) were developed for the speciation of iAs in rice samples. After microwave-assisted digestion, the As(III) ion reacted with diethyldithiophosphoric acid (DDTP) to form an As-DDTP complex and was extracted at the same time. Some parameters affecting digestion, complex formation, and extraction were studied and optimised. Under the optimised conditions, a detection limit of 0.2 µg kg(-1) with a correlation coefficient of 0.9901 were obtained with a calibration curve in the range of 0.5-200 µg kg(-1). Total iAs was determined after reduction of As(V) to As(III) with sodium thiosulfate and potassium iodide, and As(V) was calculated by difference. The proposed extraction procedure was successfully applied for the determination of iAs ions in certified reference materials (NIST CRM 1568a and NMIJ CRM 7503a) and 10 rice samples produced in Iran and other Asian countries.

Rapid extraction and determination of amphetamines in human urine samples using dispersive liquid-liquid microextraction and solidification of floating organic drop followed by high performance liquid chromatography.

A novel, rapid, simple and sensitive dispersive liquid-liquid microextraction method based on the solidification of floating organic drop (DLLME-SFO) combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) was used to determine amphetamine and methamphetamine in urine samples. The factors affecting the extraction efficiency of DLLME-SFO such as the kind and volume of the extraction and the disperser solvents, effect of concentration of K2CO3 and extraction time were investigated and the optimal extraction conditions were established. Under the optimum conditions (extraction solvent: 30.0µl 1-undecanol; disperser solvent: 300µl acetonitrile; buffer concentration: 2% (w/v) K2CO3 and extraction time: 1min), calibration curves are linear in the range of 10-3000µgl(-1) and limit of detections (LODs) are in the range of 2-8µgl(-1). The relative standard deviations (RSDs) for 100µgl(-1) of amphetamine and methamphetamine in diluted urine are in the range of 6.2-7.8% (n=7). The method was successfully applied for the determination of amphetamine and methamphetamine in the actual urine samples. The relative recoveries of urine samples spiked with amphetamine and methamphetamine are 87.8-113.2%. The obtained results show that DLLME-SFO combined with HPLC-UV is a fast and simple method for the determination of amphetamine and methamphetamine in urine.

Determination of fenvalerate in tomato by ultrasound-assisted solvent extraction combined with dispersive liquid-liquid microextraction.

Ultrasound-assisted solvent extraction (UASE) combined with dispersive liquid-liquid microextraction based on the solidification of floating organic drop (DLLME-SFO) has been developed for extraction and determination of fenvalerate from tomato samples. Fenvalerate was determined by high-performance liquid-liquid chromatography-ultraviolet detector. Effects of parameters such as type and volume of extraction solvent in the UASE stage, sonication time, type and volume of extraction solvent and disperser solvent in the DLLME-SFO stage, salt addition and pH effect on extraction were studied and optimized. Under the optimum conditions, the calibration graph was linear in the range of 5-500 µg kg(-1) with a detection limit of 0.6 µg kg(-1). The relative standard deviation for five replicate measurements of 100 µg kg(-1) of fenvalerate was 6.5%. The relative recovery of fenvalerate in different tomato samples at a spiking level of 10, 20 and 50 µg kg(-1) is in the range of 93.5-108%. The obtained results show that UASE-DLLME-SFO is a sensitive, fast and simple method for the determination of fenvalerate in tomato samples.

Estimation of esophageal cancer incidence in Tehran by log- linear method using population-based cancer registry data.

BACKGROUND: Having knowledge or estimation of cancer incidence is necessary for planning and implementation of any cancer prevention and control programs. Population-based registries provide valuable information to achieve these objectives but require extra techniques to estimate the incidence rate. The present study aimed to estimate the esophageal cancer incidence using a log-linear method based on Tehran population-based cancer registry data. MATERIALS AND METHODS: New cases of esophageal cancer reported by three sources of pathology reports, medical records, and death certificates to Tehran Metropolitan Area Cancer Registry Center during 2002-2006 were entered into the study and the incidence rate was estimated based on log-linear models. We used Akaike statistics to select the best-fit model. RESULTS: During 2002-2006, 1,458 new cases of esophageal cancer were reported by the mentioned sources to the population-based cancer registry. Based on the reported cases, cancer incidence was 4.5 per 100,000 population and this was estimated to be 10.5 per 100,000 by the log-linear method. CONCLUSIONS: Based on the obtained results, it can be concluded that an estimated incidence for 2004 of 8.3 per 100,000 population could be a good benchmark for the incidence of esophageal cancer in the population of Tehran metropolis.

Dispersive liquid-liquid microextraction followed by high-performance liquid chromatography-ultraviolet detection to determination of opium alkaloids in human plasma.

A novel, simple, rapid and sensitive dispersive liquid-liquid microextraction method based on the solidification of floating organic drop (DLLME-SFO) combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) was used to determine opium alkaloids in human plasma. During the extraction procedure, plasma protein was precipitated by using a mixture of zinc sulfate solution and acetonitrile. Some effective parameters on extraction were studied and optimized. Under the optimum conditions (extraction solvent: 30.0 µl 1-undecanol; disperser solvent: 470 µl acetone; pH: 9; salt addition: 1%(w/v) NaCl and extraction time: 0.5 min), calibration curves are linear in the range of 1.5-1000 µgl(-1) and limit of detections (LODs) are in the range of 0.5-5 µgl(-1). The relative standard deviations (RSDs) for 100 µgl(-1) of morphine and codeine, 10.0 µgl(-1) of papaverine and 20.0 µgl(-1) of noscapine in diluted human plasma are in the range of 4.3-7.4% (n=5). Finally, the method was successfully applied in the determination of opium alkaloids in the actual human plasma samples. The relative recoveries of plasma samples spiked with alkaloids are 88-110.5%. The obtained results show that DLLME-SFO combined with HPLC-UV is a fast and simple method for the determination of opium alkaloids in human plasma.

Estimation of the gastric cancer incidence in Tehran by two- source capture-recapture.

INTRODUCTION: Capture-recapture methods have been suggested for reducing costs of disease registration as well as reducing bias in incidence estimations. This study aimed to estimate the gastric cancer incidence in theTehran metropolis population during 2002-2006. MATERIALS AND METHODS: We investigated new cases of gastric cancer reported by three sources; death certificates, pathology reports, and medical records to Tehran population-based cancer registry during 2002-2006. G2 statistics and the two-source capture-recapture method were used to select the best-fitted log-linear model and to estimate incidence, respectively. EXCEL software version 2007 and SPSS software version 16 were used for this research. RESULTS: The number of reported cases was 4,463, with an average age of 68.5 (±12.9) years. We found the model that combined two sources of data including pathology reports and medical records and furthermore complemented by death certificates as the best model. The reported and the estimated incidences were 11.0 and 27.1 per 100,000 respectively. CONCLUSIONS: The incidence estimated by two- source capture-recapture method is about three times higher than the incidence reported by the sources under investigation. It is recommended to move towards the implementation of population-based cancer registration using various sources of data collection to achieve more accurate data.

Coverage, density and completeness of sources used in Tehran Metropolitan Area Cancer Registry: according to the data of esophageal cancer, 2003-2007.

BACKGROUND: The completeness of cancer registration is a major validity index of any reported cancer incidence. The present study aimed to evaluate the esophageal cancer incidence registered in the Tehran Metropolitan Area Cancer Registry. MATERIALS AND METHODS: The data on esophageal cancer abstracted from three sources of 1) pathology departments, 2) medical records, and 3) death certificates during 2003 till 2007 were utilized. The completeness of the data sources were evaluated using coverage (defined as the proportion of a community population with esophageal cancer identified by the source) and density (defined as the proportion of non-empty fields of the data by source). RESULTS: A total 1,404 cases of esophageal cancer were reported for the duration of the study. Pathology provided 771, medical records 432, and death certificates 609. The coverage was 0.55 for pathology, 0.31 for medical records, and 0.43 for death certificates. The respective density values were 0.82, 0.96 and 0.98, respectively. Pathology (0.45) was the most complete source followed by medical records (0.42), and death certificates (0.29). DISCUSSION: A low degree of completeness dictates putting more effort into case finding plus abstracting data more thoroughly.