Development of a complex-based flow injection spectrophotometric method for determination of the herbicide pinoxaden in environmental samples

A flow injection (FI) spectrophotometric method for the determination of the herbicide pinoxaden (PXD) has been proposed. PXD was converted in alkaline media with hydroxylamine hydrochloride to the hydroxamate salt. The salt was reacted with iron(III) chloride, and the absorbance of the red colored tris iron hydroxamate complex was measured at 500?nm using a FI system. The method was found to be linear between 0.5 and 40?mg?L^?1 with a molar absorptivity of 1.53?×?10^4?L?mol^?1?cm^?1. The limit of detection and limit of quantification were found to be 0.1?±?0.01?mg?L^?1 and 0.6?±?0.05?mg?L^?1, respectively. Any interference of fenoxaprop-p-ethyl (FE) was avoided by the separation of PXD by liquid chromatography with a mixture of dichloromethane and n-hexane (1?:?1) as eluent. The method was applied to the determination of PXD in soil, water, and wheat grains with percent recoveries of 98?±?2, 100?±?2, and 98?±?5, respectively. Sample throughput of 60 samples per hour was achieved under optimized conditions.     

Determination of selected semi-volatile organic compounds in water using automated online solid-phase extraction with large-volume injection/gas chromatography/mass spectrometry

A rapid, sensitive, and cost-effective analytical method was developed for the analysis of selected semi-volatile organic compounds in water. The method used an automated online solid-phase extraction technique coupled with programmed-temperature vaporization large-volume injection gas chromatography/mass spectrometry. The water samples were extracted by using a fully automated mobile rack system based on x-y-z robotic techniques using syringes and disposable 96-well extraction plates. The method was validated for the analysis of 30 semivolatile analytes in drinking water, groundwater, and surface water. For a sample volume of 10 mL, the linear calibrations ranged from 0.01 or 0.05 to 2.5 ??g·L^?1, and the method detection limits were less than 0.1 ??g·L^?1. For the reagent water samples fortified at 1.0 ??g·L^?1 and 2.0 ??g·L^?1, the obtained mean absolute recoveries were 70%?C130% with relative standard deviations of less than 20% for most analytes. For the drinking water, groundwater, and surface water samples fortified at 1.0 ??g·L^?1, the obtained mean absolute recoveries were 50%?C130% with relative standard deviations of less than 20% for most analytes. The new method demonstrated three advantages: 1) no manipulation except the fortification of surrogate standards prior to extraction; 2) significant cost reduction associated with sample collection, shipping, storage, and preparation; and 3) reduced exposure to hazardous solvents and other chemicals. As a result, this new automated method can be used as an effective approach for screening and/or compliance monitoring of selected semi-volatile organic compounds in water.     

Measuring dissolved organic carbon δ13C in freshwaters using total organic carbon cavity ring-down spectroscopy (TOC-CRDS)

This article reports the first application of coupled total organic carbon cavity ring-down spectroscopy (TOC-CRDS) for the analysis of the ??¹³C signature of dissolved organic carbon (DOC) in freshwater samples. DOC represents a major, dynamic component of the global carbon cycle. The export of DOC from soils into rivers and groundwaters may be highly climate sensitive, and much of this export may occur in ephemeral fluxes. Thus, a robust, simple and inexpensive method for the continuous determination of DOC concentration and quality is urgently needed. We detail recent advances made in the analysis of the ??¹³C signature of DOC using a TOC-CRDS system optimised for the analysis of DOC with natural abundances greater than 2.5?mg?L^?1 with no sample pre-concentration required and sample volumes of 40?mL. Precision between replicated samples was comparable to conventional analysis by gas-source isotope ratio mass spectrometry, yielding ??¹³C values with standard deviations of?±?0.5??? for DOC concentrations higher than 1.5?mg?L^?1. The utility of this technique for the analysis of DOC in samples with a broad range of compositions and concentrations (2.5?C25?mg?L^?1 DOC) is demonstrated. Since DOC ??¹³C can be measured continuously, ca. 45?min per measurement, this method enables the online monitoring of DOC in river water, water intakes and treated waters, allowing changes in DOC fluxes to be monitored in real time.     

Spectrophotometry determination of Congo red in river water samples using nanosilver

A spectrophotometric procedure for the anionic diazo dye Congo red was proposed based on nanosilver catalyzed oxidation by potassium iodate in a hydrochloric acid medium. The calibration graph is linear for 0.8–240?mg?L^?1, and the detection limit is 0.6?mg?L^?1. Most foreign ions do not interfere with the determination, except for Cu(II), Fe(III), and Cr(VI). The interferences of Cu(II) and Fe(III) could be eliminated by masking with ethylene diamine tetraacetate, and that of Cr(VI) by reducing to Cr(III) with ascorbic acid. The typical features of this procedure are that it is sensitive for Congo red, and the determination could be carried out at room temperature. It had been used for the determination of Congo red in the Ganjnameh river water sample.     

Application of water extract of slippery elm tree leaves as a natural reagent for selective spectrophotometric determination of trace amounts of molybdenum(VI) in environmental water samples

A novel spectrophotometric method for the determination of molybdenum(VI) by using a natural reagent, water extract of slippery elm tree leaves, is developed. Molybdenum(VI) reacts with this natural reagent to form an orange colored product. The formed product shows maximum absorbance at 418 nm with a molar absorptivity value of 0.57 × 10⁴ L mol^?1 cm^?1, and this method is linear in the 0.4–10 mg L^?1 concentration range. The detection limit value was found to be 0.0350 mg L^?1. The proposed method is simple, clean, low cost, selective, and sensitive. It was applied to the analytic samples with satisfactory results.     

Carbon paste electrode modified with chromium thiopental for the potentiometric flow injection analysis of chromium (III)

A chemically modified carbon paste electrode for chromium (III) based on the formation of ion-association complex of chromium with 5-ethyl-6-oxo-5-pentan-2-yl-sulfanyl-pyrimidin-4-olate (thiopental, THP) as electroactive ion-exchanger (Cr-THP) was prepared and investigated. The electrode has a linear dynamic range of 1.7?×?10^?6–1.3?×?10^?2?mol?L^?1, with a Nernstian slope of 19.6?±?0.5?mV per decade and a detection limit of 9.0?×?10^?7?mol?L^?1. It has a fast response time of <15?s and can be used for at least 7 weeks without any considerable divergence in potential. The proposed sensor revealed good selectivity for Cr(III) over a wide variety of mono-, di-, and trivalent cations and could be used in the pH range of 2.3–6.5. The proposed electrode was used in batch measurements and in flow injection analysis. The Cr-CMCPE was successfully applied for the determination of Cr(III) in real samples (wastewater of hot dip galvanizing unit and alloys). The present electrode was also used as an indicator electrode in potentiometric titration of Cr(III). The results were highly satisfactory.     

Electrochemical hydride generation of tin(II) and its determination by electrothermal atomic absorption spectrometry with in situ trapping in the graphite tube atomizer

An electrolytic hydride generation system for the determination of tin(II) by means of batch electrochemical hydride generation-electrothermal atomic absorption spectrometry (EcHG-ETAAS) with in situ trapping in a graphite tube atomizer is described. The effects of four permanent chemical modifiers – palladium, tungsten, iridium, and platinum – for graphite tube treatment on analyte absorbance and the effects of four cathode materials, i.e., Pb, Sn, Pb–Sn alloy, and glassy carbon, are checked. Three electrolytes, i.e., nitric acid, sulfuric acid, and hydrochloric acid, are examined as catholyte solutions. The influence of several parameters on EcHG is investigated using multivariate and univariate methods. Interferences of some concomitant ions are evaluated. The calibration curve is linear from 1 to 200?µg?L^?1, with a detection limit of 0.8?µg?L^?1 and a relative standard deviation of 6.2% (n?=?3) for 100?µg?L^?1 Sn(II). The proposed method was successfully applied in the analysis of real environmental water samples and reference materials, and good spiked recoveries over the range of 93.1–115% were obtained. The proposed technique provides a means for developing hydride generation of other elements.     

Effects of β-cyclodextrin on adsorption and desorption of carbofuran in soils of divergent texture

Laboratory studies were conducted to determine the adsorption/desorption equilibrium of carbofuran between four divergently textured soils and distilled water and an aqueous solution of 0.01?mol?L^?1 β-cyclodextrin using a batch equilibrium technique. The determined adsorption isotherms for silt loam soils were of L-shaped, for sandy loam soil S-shaped, in agreement with a Freundlich isotherm. In the presence of β-cyclodextrin, the adsorption of carbofuran to the four soils was lower than with distilled water. Positive hysteresis was observed in all soils with distilled water, negative hysteresis when using a solution of β-cyclodextrin as desorbent. The results indicate the potential use of β-cyclodextrin for remediation of pesticide-contaminated soils.     

Spectrophotometric and HPLC method for quantification of Loratadine on swabs for cleaning validation

Cleaning validation is a major challenge in multi-product pharmaceutical industries. UV spectrophotometric and HPLC methods have been developed and validated for determination of residual amount of Loratadine. Both methods were validated for linearity, range, accuracy, precision, and robustness. The limit of quantification was 1 mg L^?1 by UV spectrophotometric method and 0.5 mg L^?1 by HPLC method. A spike recovery study was done on a stainless steel (316 grade) plate and specific residual cleaning level (SRCL) was down to 6 μg 25.8 cm^?2. Recovery was found to be more than 70%. Both methods were simple, highly sensitive, precise, and accurate, and have potential of being useful for routine quality control.     

Ultrasound-assisted emulsification/microextraction based on solidification of trace amounts of thallium prior to graphite furnace atomic absorption spectrometry determination

In the present work, determination of ultratrace amounts of thallium in water samples was performed by ultrasound-assisted emulsification microextraction based on solidification of a floating organic drop as sample preparation method prior to furnace atomic absorption spectrometry. 1-(2-Pyridylazo)-2-naphthol was used as chelating agent. The factors influencing the complex formation and extraction, such as pH of the aqueous solution, the type and the volume of extraction solvent, the volume of chelating agent solution, and the extraction time were investigated. Under optimized conditions, the enrichment factor was 200. The calibration graph was linear from 0.2 to 10.0 μg L^?1 with a correlation coefficient of 0.9966, the detection limit was 0.03 μg L^?1 and reproducibility was ±3.3% (C = 5.0 μg L^?1, n = 8). The method was successfully applied for the determination of thallium in water samples.     

Prevalence of organochlorine pesticide residues in groundwaters of Kasargod District,India

The Kasargod District is the northernmost district of Kerala State and is bound between the north latitudes 12°02′27″ and 12°47′35″ and east longitudes 74°51′54″ and 75°25′25″. The present study highlights the contamination levels of organochlorine pesticides in open wells of the Kasargod District from 2010 to 2011. Maximum contamination of organochlorine pesticides (OCP's) was observed for endosulfan followed by hexachlorobenzene (BHC). Contamination levels of α-endosulfan were higher at Panathur (58?µg?L^?1) and next to Periya (37?µg?L^?1) in the postmonsoon season of 2010. During premonsoon 2011, the residue levels of α-endosulfan were higher at Panathady (56?µg?L^?1) followed by Rajapuram (40?µg?L^?1). Contamination levels of the BHC isomers exhibit the order of γ-BHC?>?α-BHC?>?β‐BHC, showing that γ-BHC represents 62% of the total OCP residues in premonsoon 2010. Among the studied OCP's, concentration levels of DDT were below detection limit. Maximum concentrations of the sum of all OCP residues were observed at Mulleria and Cheemeni (premonsoon 2010), followed by Panathur and Periya (postmonsoon 2010), and lowest in Panathady and Rajapuram (premonsoon 2011). Residues of OCP's were lowest in Paettikundu and Cheravatur in all the three seasons.     

A nanosilver-based spectrophotometric method for sensitive determination of methyl violet in river water

A method is reported for the determination of methyl violet in the range of 10–120 nmol L^?1. The method is based on the catalytic effect of silver nanoparticles (AgNPs) on the oxidation reaction of methyl violet by potassium bromate in acid medium. The reaction is followed spectrophotometrically by measuring the change in absorbance () at 620 nm using a fixed time method. The reaction variables were optimized in order to achieve highest sensitivity. The 3б criterion detection limit was 5 nmol L^?1, and the relative standard deviation for ten replicate determinations at a concentration of methyl violet of 15 nmol L^?1 was 0.97% (n = 10). The method was successfully applied to the determination of methyl violet in river water samples.     

A fast and reliable method for quantitative determination of total mercury in vegetables

A cloud-point extraction (CPE) process using the nonionic surfactant, polyethylene glycol tert octylphenyl ether (Triton X-114) was employed for determination of Hg(II) ions in aqueous solutions. The method is based on the ion-pairing reaction of Hg(II) with Pyronin B (PyrB⁺) in the presence of excess iodide at pH 6.0 and extraction of the complex formed. The chemical variables affecting CPE efficiency were studied, and the analytical characteristics of the method were obtained. The calibration curves were linear in the range of 1–40 μg L^?1 with the detection limits of 0.35 and 0.30 μg L^?1 at 556 and 521 nm. Selectivity was also tested. The coefficients of variation of the method are 2.4% and 5.2% for five replicate measurements of mercury at levels of 10 and 25 μg L^?1, respectively. The results obtained for two certified reference samples were in a good agreement with the certified values. The method was applied to the determination of total mercury in vegetable samples.     

Online solid phase preconcentration using EGDMA–MAA copolymer for lead determination by FAAS

A Ethylene glycol dimethacrylate (EGDMA) methacrylic acid (MAA) resin was used for preconcentration of lead at trace levels in water samples. For this purpose, a flow-injection, solid phase extraction method was developed for the determination of lead by flame atomic absorption spectrometry. Lead ions were sorbed on a EGDMA–MAA column at pH 4, followed by an elution step using 288 µL of 4.0 M nitric acid solution and determination by flame atomic absorption spectrometry. Optimum conditions for quantitative sorption involving the pH, sample volume, loading and elution flow rates, eluent type, and volume were investigated. A 868-fold enrichment factor could be reached. The detection limit for the water samples, estimated from the noise on the signal obtained for 250 mL of 10 µg L^?1 loaded at 4.9 mL min^?1 was 1.04 µg L^?1. The method was applied for lead determination in river water samples collected in Edirne, Turkey. Recoveries of spiked solutions (10 µg L^?1) to river water samples were quantitative. Finally, the method was validated by the analysis of certified reference material SRM 2704 (Buffalo River Sediment).     

Ligand-less in situ surfactant-based solid phase extraction for preconcentration of silver from natural water samples prior to its determination by atomic absorption spectroscopy

A simple and rapid ligand-less in situ surfactant-based solid phase extraction method for preconcentration of silver from water samples is developed. In this method, a cationic surfactant containing a proper alkyl group (n-dodecyltrimethylammonium bromide) is dissolved in the aqueous sample and then a proper ion-pairing agent (ClO₄^?) is added. Due to the interaction between surfactant and ion-pairing agent, solid particles are formed and used for adsorption of silver carbonate. After centrifugation, the sediment is dissolved in 2.0 mL 1 M HNO₃ in ethanol and then aspirated directly into the flame atomic absorption spectrometer. Variables affecting the extraction efficiencies such as pH, concentrations of surfactant and CO₃^2?, ion pair concentration, and extraction time, are optimized. Under such conditions, the calibration curve is linear from 3 to 700 μg L^?1. Detection limit is 1.1 μg L^?1 with an enrichment factor of 37. The relative standard deviation for eight replicate measurements of 100 μg L^?1 is 2.1%. The method has been applied for the determination of silver in water samples.     

Quantification of TiO2 and ZnO nanoparticles in wastewater using inductively coupled plasma optical emission spectrometry

Abstract

The applicability of inductively coupled plasma optical emission spectrometry has been examined for determination titanium dioxide and zinc oxide nanoparticles in industrial wastewater samples. The extraction and preconcentration of the nanoparticles were achieved using ligandless ultrasound-assisted surfactant-based dispersive liquid–liquid microextraction. Under optimized conditions, the developed method had limits of detection (LOD) of 2.7?ng L^?1 for Ti and 3.6?ng L^?1 for Zn resulting from dissolved TiO₂ and ZnO nanoparticles. The relative standard deviation values for intraday precision were 2.5% and 3.1% for TiO₂ and ZnO, while the interday precision was 4.5% and 5.0%. Percentage recoveries ranging from 98% to 100% were obtained. Finally, the applicability of the method was examined by analyzing spiked samples and wastewater samples collected from textile, cosmetic and paint industries.     

ELISA determination of Aflatoxin M1 in milk and dairy products in Pakistan

A highly sensitive competitive ELISA was standardized to determine aflatoxin M₁ (AFM₁) in milk and dairy samples randomly collected from Faisalabad city, using Riedel-de-Haen, Aflatoxin M₁ ELISA Systems, (Art–No. 45169). Standards of 5, 10, 25, 50, and 100 ng L^?1 AFM₁ in sample/standard buffer were used in optimizing anti-AFM₁ antibodies and peroxidase–AFM₁ conjugate. Linear standard curve showed increase in concentration (log C) accompanied by decrease in maximal absorbance (%B/B₀) values (%B/B₀ = 124.3 ? 45.0 log C) with highly significant negative correlation (?0.973). The middle of the test (50% B/B₀) was at 30 ng L^?1 with 6.7 ng L^?1 the lowest detection limit (90% B/B₀). Duplicate analysis of 41 samples showed AFM₁ levels below EC permissible limits (50 ng L^?1) with maximums of 40, 13, and 7.4 ng L^?1 in milk, yogurt and butter, respectively. However, possibility of exceeding limits cannot be excluded, and demands regular monitoring.     

Evaluation of the effect of antimicrobials in marine cultures,using the copepod Acartia tonsa as a bioindicator

Cultures of the copepod Acartia tonsa are used both in aquaculture and ecotoxicology studies. However, the cultivation of these crustaceans at high densities results in the proliferation of microorganisms that can affect the organisms of interest, leading to illness or death. Antimicrobials inhibit microbial growth and may favour the cultivated species, aiding the development of ecological studies. This study investigated the potential of antimicrobials (antibiotic + antifungal) to inhibit bacteria and fungi when applied to marine zooplankton cultures, using the copepod A. tonsa as a bioindicator of acute toxicity. Treatment with 0.025?g?L^?1 of penicillin G potassium + 0.08?g?L^?1 of streptomycin sulphate + 0.04?g?L^?1 of neomycin sulphate + 0.005?g?L^?1 of nystatin resulted in 95% bacterial inhibition (after 12?h of exposure); however, after this time, the inhibitory effect was lost. The antimicrobial combination tested in this study prevented colonisation by fungi until 168?h after exposure, without causing acute toxicity to A. tonsa. Thus, it has potential for use in marine cultures of less sensitive organisms.     

Impact of solids on biphasic biodegradation of phenanthrene in the presence of hydroxypropyl-<Emphasis Type="Italic">β</Emphasis>-cyclodextrin (HPCD)

The consequence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of great concern. The hydrophobic properties of PAHs significantly impact phase distribution causing limited bioavailability. Enhanced biodegradation has been extensively carried out by surfactants and the redeployment effect was recognized. However, the quantitative relationship concerning the impact of solids was rarely reported. A batch of biphasic tests were carried out by introducing Mycobacterium vanbaalenii PYR-1 and hydroxypropyl-β-cyclodextrin (HPCD) into a mixture of phenanthrene solution and various glass beads (GB37-63, GB105-125, and GB350-500). The comparative results demonstrated that HPCD had little effect on microbial growth and was not degradable by bacterium. A model was proposed to describe the biodegradation process. The regression results indicated that the partition coefficient k _d (1.234, 0.726 and 0.448 L·g^?1) and the degradation rate k (0 mmol·L^?1: 0.055, 0.094, and 0.112; 20 mmol·L^?1: 0.126, 0.141, and 0.156; 40 mmol·L^?1: 0.141, 0.156 and 0.184 d^?1) were positively and negatively correlated with the calculated total surface area (TSA) of solids, respectively. Degradation enhanced in the presence of HPCD, and the enhancing factor f was calculated (20 mmol·L^?1: 15.16, 40.01, and 145.5; 40 mmol·L^?1: 13.29, 37.97, and 138.4), indicating that the impact of solids was significant for the enhancement of biodegradation.     

A novel ligand for cloud point extraction to determine gold content in ore samples

Gold is a valuable metal occurring usually at very low concentrations in complex natural samples. Gold analysis thus needs preconcentration methods. Classical liquid–liquid extraction involves hazardous organic solvents. Alternatively, cloud point extraction involves non-toxic and nonvolatile surfactants. Here, we analyzed ore samples. The complex of Au(III) with sulphapyridylazo resorcin was extracted by the cloud point method. Concentrations were measured by flame atomic absorption spectrometry. We tested the effects of pH, reagent concentration, Triton X-100 surfactant concentration, equilibration temperature and time. Results show that the best detection limit of the method was 0.48 µg L^?1 for Au with a preconcentration factor of 31 times. Calibration is linear in range of 6.4–2,000 µg L^?1, and relative standard deviations are lower than 5 %. Quantum chemical computations reveal the plausible structure of the gold–ligand complex. This report represents the first determination of gold using sulphapyridylazo resorcin as a ligand.