Application of zirconium–iridium permanent modifier for the simultaneous determination of lead, cadmium, arsenic, and nickel in atmospheric particulate matter by multi-element electrothermal atomic absorption spectrometry

A novel and robust method for the simultaneous determination of lead, cadmium, arsenic, and nickel in atmospheric particulate matter by multi-element electrothermal atomic absorption spectrometry was developed, using zirconium–iridium coating as permanent modifier (140 μg Zr and 4 μg Ir). After 300 atomization cycles, it was necessary to add 2 μg of Ir. Due to the varying concentrations of Pb in atmospheric particulate matter, lead was monitored at two wavelengths, at the less sensitive line of 261.4 nm for high concentration samples (>20 μg?L^?1) or at 283.3 nm for the low concentration samples. Matrix-matched calibration had to be performed for quantitative recoveries (96–102 %). Following this approach, the four elements were determined in atmospheric particulate matter samples from an industrial area near the city of Athens in two different time periods (cold–warm) with limits of detection of 5.5 ng?m^?3 for Pb at 261.4 nm and 0.29 ng?m^?3 at 283.3 nm, 0.019 ng?m^?3 for Cd, 0.14 ng?m^?3 for As, and 0.22 ng?m^?3 for Ni. Lead, Cd, and As levels were very low, whereas Ni content was at comparable levels with other areas worldwide.     

The use of silica gel modified with allyl 6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate for selective separation and preconcentration of lead in environmental samples

The aim of the present work is the assessment of a new sorbent, prepared using silica gel coated with a pyrimidine derivative (allyl 6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate), for extraction and preconcentration trace amount of lead from different samples prior to determination by flame atomic absorption spectrometry. Common coexisting ions did not interfere with the separation and determination of lead at pH?6, so that lead ion completely adsorbed on the column. The limit of detection based on three times the standard deviation of the blank was found to be 0.53 ng?mL^?1 in original solution. Obtained sorption capacity for 1 g sorbent was 5.0 mg Pb. The linearity was maintained in the concentration range of 0.1–30.0 ng?mL^?1 for the concentrated solution. Eight replicate determinations of 2.0 μg?mL^?1 of lead in the final solution gave relative standard deviation of ±2.6 %. The proposed method was successfully applied to the determination trace amounts of lead in the environmental samples such as carrot, rice, zardchoobe, and real water samples.     

Hazard assessment of metals in invasive fish species of the Yamuna River,India in relation to bioaccumulation factor and exposure concentration for human health implications

Monitoring of heavy metals was conducted in the Yamuna River considering bioaccumulation factor, exposure concentration, and human health implications which showed contamination levels of copper (Cu), lead (Pb), nickel (Ni), and chromium (Cr) and their dispersion patterns along the river. Largest concentration of Pb in river water was 392 μg L^?1; Cu was 392 μg L^?1 at the extreme downstream, Allahabad and Ni was 146 μg L^?1 at midstream, Agra. Largest concentration of Cu was 617 μg kg^?1, Ni 1,621 μg kg^?1 at midstream while Pb was 1,214 μg kg^?1 at Allahabad in surface sediment. The bioconcentration of Cu, Pb, Ni, and Cr was observed where the largest accumulation of Pb was 2.29 μg kg^?1 in Oreochromis niloticus and 1.55 μg kg^?1 in Cyprinus carpio invaded at Allahabad while largest concentration of Ni was 174 μg kg^?1 in O. niloticus and 124 μg kg^?1 in C. carpio in the midstream of the river. The calculated values of hazard index (HI) for Pb was found more than one which indicated human health concern. Carcinogenic risk value for Ni was again high i.e., 17.02?×?10^?4 which was larger than all other metals studied. The results of this study indicated bioconcentration in fish due to their exposures to heavy metals from different routes which had human health risk implications. Thus, regular environmental monitoring of heavy metal contamination in fish is advocated for assessing food safety since health risk may be associated with the consumption of fish contaminated through exposure to a degraded environment.     

Rapid spectrophotometric determination of trace amounts of palladium in water samples after dispersive liquid–liquid microextraction

A simple, rapid, and efficient dispersive liquid–liquid microextraction method, followed by UV–Vis spectrophotometry was developed for the preconcentration and determination of Pd ions in water samples. Pd ions react with α-furildioxime (chelating agent) to form a hydrophobic complex. Various parameters were altered to study and optimize their effects on the extraction efficiency, such as pH, ligand concentration, the type and volume of extraction and dispersive solvents, extraction time, and salt concentration. Under optimized conditions, the method exhibited an enrichment factor (C _org/C _aq) of 25 and recovery more than 98 % within a very short extraction time. The linearity of the method ranged from 10 to 200 μg?L^?1. The limit of detection was 1.1 μg?L^?1. The relative standard deviation for the concentration of 100 μg?L^?1 of Pd was 2.3 % (n?=?10). Finally, the developed method was successfully applied to the extraction and determination of Pd in tap, river, mineral, and sea water samples.     

Occurrence of mycotoxins in feed samples in Burdur Province, Turkey

The aim of this study was to evaluate the incidence of total aflatoxin (AF), ochratoxin A, T-2 toxin, deoxynivalenol (DON), zearalenone (ZEA), and fumonisin (FB) in dairy cattle, beef cattle, and lamb–calf feeds. A total of 180 dairy cattle, beef cattle, and lamb–calf feeds (60 samples each) were randomly collected from farms, feed mills, and villages in Burdur province, between September 2006 and August 2007. All samples were analyzed by the competitive Enzyme Linked Immuno Sorbent Assay (ELISA). The most frequent mycotoxin detected was total AF, which was found in 108 samples (60 %) in concentrations ranging from 3.82 to 116.83 μg?kg^?1, followed by DON that was detected in 87 samples (48.3 %), in concentrations ranging from 18.50 to 500 μg?kg^?1. Ochratoxin A (OTA), T-2 toxin, ZEA, and FB were found in 84 (46.7 %), 85 (47.2 %), 57 (31.7 %), and 19 (10.6 %) samples, respectively, in concentrations of 1.01 to 15.85 μg?kg^?1 for OTA, 3.85 to 52.36 μg?kg^?1 for T-2 toxin, 2.10 to 29.30 μg?kg^?1 for ZEA, and 2.69 to 4.96 mg?kg^?1 for FB. It was concluded that feed samples in Burdur province were contaminated by mycotoxins, and the levels of total aflatoxin in the samples were considered a risk to animal health.     

Flow injection spectrophotometric determination of methamidophos using online hydrolysis

A new protocol for the online spectrophotometric determination of methamidophos has been developed. The method is based on online hydrolysis of methamidophos, and the resulting hydrolyzed product is reacted with sodium nitroproside to form a colored complex. The calibration curve is linear over the concentration range of 0.5–20 μgml^?–?1, with a molar absorptivity of 2.5×10⁴ L mol^?1 cm^?1. The method is fast and reproducible with a sample throughput of 90 samples/h. The method is successfully applied to formulations and real samples.     

Ultra-sensitive quantification of copper in food and water samples by electrochemical adsorptive stripping voltammetry

A new electrochemical adsorptive stripping voltammetry method was developed for the determination of trace amounts of copper in food and water samples. The study of electrochemical behavior of Cu ion indicated that Cu(II) and Schiff base formed a complex in H₃BO₄–NaOH buffer solution (pH?=?7.25). An accumulation potential of ?100 mV (vs Ag/AgCl) was applied while the solution was stirred for 60 s. The response curve was recorded by scanning the potential, and the peak current of ?0.31 V (vs Ag/AgCl) was recorded. The peak current and concentration of copper accorded with linear relationship in the range of 0.04–120 ng mL^?1. The relative standard deviation (for 12 ng mL^?1 of copper) was 1.73 %, and the detection limit was 0.007 ng mL^?1. The possible interference of some common ions was studied. The proposed method was applied to the determination of copper in water, rice, wheat, tea, milk, and tomato with satisfactory results.     

Solid phase extraction and determination of Cr(III) by spectrophotometry using cefaclor as a complexing reagent and FAAS

The present study reports on the application of modified groundnut shell as a new, easily prepared, and stable sorbent for the extraction of trace amount of Cr(III) in aqueous solution. 2-Hydroxybenzaldiminoglycine was immobilized on groundnut shells in alkaline medium and then used as a solid phase for the column preconcentration of Cr(III). The elution was carried out with 3 mL of 2 mol?L^?1 HCl. The amount of eluted Cr(III) was determined by spectrophotometry using cefaclor as a complexing reagent and by flame atomic absorption spectrometry (FAAS). Different experimental variables such as pH, amount of solid sorbent, volume and concentration of eluent, sample and eluent flow rate, and interference of other metal ions on the retention of Cr(III) were studied. Under the optimized conditions, the calibration curves were found to be linear over the concentration range of 13–104 and 10–75 μg?L^?1 with a detection limit of 3.64 and 1.24 μg?L^?1 for spectrophotometric method and FAAS, respectively. An enrichment factor of 200 and RSD of ±1.19–1.49 % for five successive determinations of 25 μg?L^?1 were achieved. The column preconcentration was successfully applied to the analysis of tap water and underground water samples.     

Validation of spectrophotometric method for Se(IV) determination: analytical applications

As selenium is an important part of the antioxidant enzymes and also because there are several studies suggesting a possible link between cancer and selenium deficiency, this paper presents a spectrophotometric method for the assay of Se(IV), using N,N-diethyl-p-phenylenediamine monohydrochloride as reagent. The proposed method is based on the reaction between the selenium and potassium iodide in low acidic medium, when iodine is released. This last product will further oxidise the new reagent. The final obtained product is strongly coloured in red and has an absorption maximum at 552 nm and molar extinction coefficient (ε) of 6.1?×?10⁴ L mol^?1 cm^?1. The optimum working conditions were established, and the developed method was validated, being characterised by a good linearity (in the range of 0.5–3.0 μg/mL), a limit of detection (0.0573 μg/mL) and a limit of quantification (0.1737 μg/mL). At the same time, the repeatability, the precision of the method and the accuracy were established. The proposed and validated method was applied with good results for the determination of Se(IV) in spring and bottled water from Iasi and also in pharmaceutical and cosmetic products.     

Dissipation and residues of bispyribac-sodium in rice and environment

The dissipation and residues of bispyribac-sodium in rice cropping system were studied. Bispyribac-sodium residues were extracted by a simple analytical method based on QuEChERs and detected by LC-MS/MS. The limit of detection for bispyribac-sodium of this method was 0.375?×?10^?3 ng. The limit of quantification (LOQ) was 5.0 μg/kg for rice plant samples, 2.0 μg/kg for rice hull, 0.2 μg/kg for water, and 0.1 μg/kg for soil and husked rice samples. The average recoveries of bispyribac-sodium ranged from 74.7 to 108 %, with relative standard deviations less than 13 %. The half-lives of bispyribac-sodium in rice plant, water, and soil were in the range of 1.4–5.6 days. More than 90 % of bispyribac-sodium residue dissipated within 5 days. The final residues of bispyribac-sodium in rice were all below LOQ at harvest time.     

Dissipation kinetics and assessment of processing factor for chlorpyrifos and lambda-cyhalothrin in cardamom

The dissipation kinetics and method for estimation of residues of chlorpyrifos and lambda-cyhalothrin in cardamom were studied and developed. The limit of detection and limit of quantitation arrived for the compounds were 0.01 and 0.025 μg?g^?1, respectively. Gas chromatographic response of chlorpyrifos and lambda-cyhalothrin residues was linear in the range of 0.01–0.50 μg?g^?1 and the mean recovery obtained was 97.3 % for chlorpyrifos and 98.9 % for lambda-cyhalothrin with satisfactory relative standard deviation values. The mean initial residues of chlorpyrifos applied at a concentration of 0.05 % in cardamom was 2.5 μg?g^?1 and the residue was 8.1 μg?g^?1 after processing, with a processing factor of 3.24, while lambda-cyhalothrin when applied at 0.0025 % resulted in initial residues of 1.63 μg?g^?1 that magnified to 4.86 μg?g^?1 on curing, with a processing factor of 2.98. The half-life of chlorpyrifos was in the range of 5.1–5.24 days while that of lambda-cyhalothrin was in the range of 4.40–4.55 days. The processing factor arrived at in the above experiment lead to the conclusion that the residues of chlorpyrifos got magnified to 3.24–3.68 times and that of lambda-cyhalothrin got magnified to 2.98–3.46 times of initial residues, consequent to loss of weight due to dehydration during curing.     

Temporal variability in water quality parameters—a case study of drinking water reservoir in Florida, USA

Our objective was to evaluate changes in water quality parameters during 1983–2007 in a subtropical drinking water reservoir (area: 7 km²) located in Lake Manatee Watershed (area: 338 km²) in Florida, USA. Most water quality parameters (color, turbidity, Secchi depth, pH, EC, dissolved oxygen, total alkalinity, cations, anions, and lead) were below the Florida potable water standards. Concentrations of copper exceeded the potable water standard of <30 μg?l^?1 in about half of the samples. About 75 % of total N in lake was organic N (0.93 mg?l^?1) with the remainder (25 %) as inorganic N (NH₃-N: 0.19, NO₃-N: 0.17 mg?l^?1), while 86 % of total P was orthophosphate. Mean total N/P was <6:1 indicating N limitation in the lake. Mean monthly concentration of chlorophyll-a was much lower than the EPA water quality threshold of 20 μg?l^?1. Concentrations of total N showed significant increase from 1983 to 1994 and a decrease from 1997 to 2007. Total P showed significant increase during 1983–2007. Mean concentrations of total N (n?=?215; 1.24 mg?l^?1) were lower, and total P (n?=?286; 0.26 mg?l^?1) was much higher than the EPA numeric criteria of 1.27 mg total N l^?1 and 0.05 mg total P l^?1 for Florida’s colored lakes, respectively. Seasonal trends were observed for many water quality parameters where concentrations were typically elevated during wet months (June–September). Results suggest that reducing transport of organic N may be one potential option to protect water quality in this drinking water reservoir.     

The use of rapidly synergistic cloud point extraction for the separation and preconcentration of trace amounts of Ni (II) ions from food and water samples coupling with flame atomic absorption spectrometry determination

A novel improved preconcentration method known as rapidly synergistic cloud point extraction (RS-CPE) was established for nickel preconcentration and determination prior to its determination by flame atomic absorption spectrometry. In this work, the traditional CPE pattern was changed and greatly simplified in order to be applicable in metal extraction and detection. This method was accomplished in room temperature in 1 min. Non-ionic surfactant Triton X-114 was used as extractant. Octanol worked as cloud point revulsant and synergic reagent. The various parameters affecting the extraction and preconcentration of nickel such as sample pH, 2,2′-Furildioxime concentration, amounts of octanol, amounts of Triton X-114, type of diluting solvent, extraction time, and ionic strength were investigated and optimized. Under optimal conditions, the calibration curve showed an excellent linearity in the concentration range of 2–200 μg L^?1, and the limit of detection was 0.6 μg L^?1 for nickel. The developed method was successfully applied for the determination of nickel in food and water samples. The results showed that, the proposed method can be used as a cheap, rapid, and efficient method for the extraction and preconcentration of nickel from real samples.     

Assessment of the labile fractions of copper and zinc in marinas and port areas in Southern Brazil

The dissolved labile and labile particulate fractions (LPF) of Cu and Zn were analyzed during different seasons and salinity conditions in estuarine waters of marina, port, and shipyard areas in the southern region of the Patos Lagoon (RS, Brazil). The dissolved labile concentration was determined using the diffusive gradients in thin films technique (DGT). DGT devices were deployed in seven locations of the estuary for 72 h and the physicochemical parameters were also measured. The LPF of Cu and Zn was determined by daily filtering of water samples. Seasonal variation of DGT–Cu concentrations was only significant (p?<?0.05) at one shipyard area, while DGT–Zn was significant (p?<?0.05) in every locations. The LPF of Cu and Zn concentrations demonstrated seasonal and spatial variability in all locations, mainly at shipyard areas during high salinity conditions. In general, except the control location, the sampling locations showed mean variations of 0.11–0.45 μg?L^?1 for DGT–Cu, 0.89–9.96 μg?L^?1 for DGT–Zn, 0.65–3.69 μg?g^?1 for LPF–Cu, and 1.35–10.87 μg?g^?1 for LPF–Zn. Shipyard areas demonstrated the most expressive values of labile Cu and Zn in both fractions. Strong relationship between DGT–Zn and LPF–Zn was found suggesting that the DGT–Zn fraction originates from the suspended particulate matter. Water salinity and suspended particulate matter content indicated their importance for the control of the labile concentrations of Cu and Zn in the water column. These parameters must be taken into consideration for comparison among labile metals in estuaries.     

The high potential of Pelargonium roseum plant for phytoremediation of heavy metals

The major objective of this investigation was to evaluate the potential of scented geraniums, Pelargonium roseum, to uptake and accumulate heavy metals nickel (Ni), cadmium (Cd), or lead (Pb). For this, plants were grown in an artificial soil system and exposed to a range of metal concentrations over a 14-day treatment period. Then, metals from the entire biomass were extracted. The results showed that scented geranium plants accumulated in excess of 20,055 mg of Ni kg^?1 dry weight (DW) of root and 10,889 mg of Ni kg^?1 DW of shoot, and in excess of 86,566 mg of Pb kg^?1 DW for roots and 4,416 mg of Pb kg^?1 DW for shoots within 14 days. Also, the uptake and accumulation of cadmium in roots of scented geranium plants increased with the exposure at low (250, 500 mg?L^?1) and medium level (750 mg?L^?1) followed by a decline at the highest level (1,000 mg?L^?1). The highest accumulation in roots (31,267 mg?kg^?1 DW) was observed in 750 mg?L^?1 cadmium treatment. In the shoots of scented geraniums, the highest amount of metal accumulation (1,957 mg?kg^?1 DW) was detected at 750 and 1,000 mg?L^?1 of cadmium in the culture solution. Finally, since the high concentrations of Ni or Pb accumulated in shoots of scented geranium has far exceeded 0.1 % DW and for Cd has far exceeded 0.01 % DW, P. roseum is a new hyperaccumulator species for these metals and can be used in phytoremediation industry.     

Single drop microextraction and gas chromatography–mass spectrometry for the determination of diflufenican, mepanipyrim, fipronil, and pretilachlor in water samples

An analytical method for the determination of diflufenican, mepanipyrim, pretilachlor, and fipronil in water samples was developed using single drop microextraction in the direct immersion mode and gas chromatography–mass spectrometry. A factorial fractionated design of type 2^6–1 at two levels was performed, to study the influence of experimental variables such as ionic strength, pH, agitation speed, extraction time, drop volume, and sample volume. To establish the optimal conditions for the variables that were significant, a Doehlert design was performed. The optimum conditions of extraction were 1 μL of heptane immersed in 4.0 mL of sample with continuous agitation at 500 rpm for 30 min at room temperature. The developed method proved to have good linearity for the range studied. The detection limits were 0.07 μg L^?1 for diflufenican, 0.03 μg L^?1 for mepanipyrim, 0.08 μg L^?1 for pretilachlor, and 1.39 μg L^?1 for fipronil. The method was validated on river water samples, showing the absence of matrix effect and recoveries ranged from 90.1 to 107.8 %. The results show that the method developed is accurate, sensitive, rapid, simple, and low cost, so it is recommended for application in the analysis of these different classes of pesticides in water samples.     

Mapping of fluoride endemic area and assessment of F−1 accumulation in soil and vegetation

The prevalence of fluorosis is mainly due to the consumption of more fluoride (F^?1) through drinking water, vegetables, and crops. The objective of the study was mapping of F^?1 endemic area of Newai Tehsil, Tonk district, Rajasthan, India. For the present study, water, soil (0–45 cm), and vegetation samples were collected from 17 villages. Fluoride concentration in water samples ranged from 0.3 to 9.8 mg/l. Out of 17 villages studied, the amounts of F^?1 content of eight villages were found to exceed the permissible limits. Labile F^?1 content and total F^?1 content in soil samples ranges 11.00–70.05 mg/l and 50.3–179.63 μg g^?1, respectively. F^?1 content in tree species was found in this order Azadirachta indica 47.32–55.76 μg g^?1 > Prosopis juliflora 40.16–49.63 μg g^?1 > Acacia tortilis 34.39–43.60 μg g^?1. While in case of leafy vegetables, F^?1 content order was Chenopodium album 54.23–98.42 μg g^?1 > Spinacea oleracea 30.41–64.09 μg g^?1 > Mentha arvensis 35.48–51.97 μg g^?1. The order of F^?1 content in crops was found as 41.04 μg g^?1 Pennisetum glaucum > 13.61 μg g^?1 Brassica juncea > 7.98 μg g^?1 Triticum sativum in Krishi Vigyan Kendra (KVK) farms. Among vegetation, the leafy vegetables have more F^?1 content. From the results, it is suggested that the people of KVK farms should avoid the use of highly F^?1 containing water for irrigation and drinking purpose. It has been recommended to the government authority to take serious steps to supply drinking water with low F^?1 concentration for the fluorosis affected villages. Further, grow more F^?1 hyperaccumulator plants in F^?1 endemic areas to lower the F^?1 content of the soils.     

Application of cold-induced aggregation microextraction as a fast,simple, and organic solvent-free method for the separation and preconcentration of Se(IV) in rice and various water samples

The developed method is based on cold-induced aggregation microextraction of Se(IV) using the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as an extractant followed by spectrophotometry determination. The extraction of Se(IV) was performed in the presence of dithizone as the complexing agent. In this method, a very small amount of 1-butyl-3-methylimidazolium hexafluorophosphate was added to the sample solution containing Se-dithizone complex. Then, the solution was kept in a thermostated bath at 50 °C for 4 min. Subsequently, the solution was cooled in an ice bath and a cloudy solution was formed. After centrifuging, the extractant phase was analyzed using a spectrophotometric detection method. Some important parameters that might affect the extraction efficiency were optimized (HCl, 0.6 mol L^?1; dithizone, 4.0?×?10^?6 mol L^?1; ionic liquid, 100 μL). Under the optimum conditions, good linear relationship, sensitivity, and reproducibility were obtained. The limit of detection (LOD) (3S_b/m) was 1.5 μg L^?1, and the relative standard deviation (RSD) was 1.2 % for 30 μg L^?1 of Se(IV). The linear range was obtained in the range of 5–60 μg L^?1. It was satisfactory to analyze rice and various water samples.     

Heavy metal in water and aquatic organisms from different intertidal ecosystems,Persian Gulf

Intertidal ecosystems are being damaged by anthropogenic activities, particularly in the developing countries. In this study, the load of heavy metals was determined in water, fish, shrimp, and crab collected from four intertidal ecosystems, including coral reef, rocky shore, mangrove forest, and muddy habitat along the Persian Gulf coasts. Generally, the sequence of metal accumulation in the water of coral reef and mangrove forest was Ni > Pb > V > Cd > As > Hg, whereas in muddy habitats and rocky shores, the sequence was Ni > Pb > V > Cd > Hg > As and Ni > V > Pb > As > Hg > Cd, respectively. Water of the coral reef had the highest level of Ni (97.44 μg l^?1), Pb (3.92 μg l^?1), V (10.42 μg l^?1), Cd (3.92 μg l^?1), As (1.87 μg l^?1), and Hg (0.74 μg l^?1). For the most part, the highest concentrations of the studied metals were found in the liver and the gills of Johnius belangerii and the hepatopancreas of Portunus pelagicus and Metapenaus affinis collected from the coral reef ecosystem.     

A very sensitive flow-injection spectrophotometric determination method for iron (II) and total iron using 2′, 3, 4′, 5, 7-pentahydroxyflavone

In this study, an ultra-sensitive and highly selective, rapid flow-injection spectrophotometric method for the determination of iron (II) and total iron has been proposed. The method was based on the reaction between iron (II) and 2′, 3, 4′, 5, 7-pentahydroxyflavone in slightly acidic solution with a strong absorption at 415 nm. The carrier solution used was 1?×?10^?5 M 2′, 3, 4′, 5, 7-pentahydroxyflavone in 0.1 M HAc/Ac^? buffer solution at pH 4.5. Parameters that affect simultaneously the determination of iron (II) and interfering ions were tested. The relative standard deviation for the determination of 50 μg L^?1 iron (II) was 0.85 % (n?=?10), and the limit of detection (blank signal plus three times the standard deviation of the blank) was 3 μg L^?1, both based on injection volumes of 20 μL. The method has been successfully applied to the determination of iron (II) and total iron in water samples and ore samples. The method was verified by analysing a certified reference material Zn/Al/Cu 43XZ3F.