Determination of three alkylphenol isomers in various water samples using a new HPLC method based on a duet stationary phase

The level of three alkylphenols (APs) 4-nonylphenol, 4-octylphenol and 4-tert-octylphenol was monitored in various water samples using a new developed and validated HPLC method. The HPLC method employed a column with a mixed-mode stationary phase (C18/SCX) using a mobile phase of water to methanol?=?15:85 (v/v) delivered at a flow rate of 1 mL/min at room temperature. Both diode array, DAD and fluorescence, FLD detectors were employed. The method is linear when APs concentration ranged from 0.025 to 0.5 μg/mL with a DAD detection at 279 nm and between 0.0008 and 0.1 μg/mL when the detection was made by FLD (excitation at 220 nm, emission at 315 nm). The limit of detection and limit of quantitation for alkylphenols were found to be 5 and 15 ng/mL, respectively (detection by DAD). The method was employed with good results for the determination of APs in the presence of polycyclic aromatic hydrocarbons in various water samples.     

HPLC-FLD determination of 4-nonylphenol and 4-<Emphasis Type="Italic">tert</Emphasis>-octylphenol in surface water samples

A simple, sensitive and reliable HPLC-FLD method for the routine determination of 4-nonylphenol, 4-NP and 4-tert-octylphenol, 4-t-OP content in water samples was developed. The method consists in a liquid–liquid extraction of the target analytes with dichloromethane at pH  3.0–3.5 followed by the HPLC-FLD analysis of the organic extract using a Zorbax Eclipse XDB C8 column, isocratic elution with a mixed solvent acetonitrile/water 65:35, at a flow rate of 1.0 mL/min and applying a column temperature of 40°C. The method was validated and then applied with good results for the determination of 4-NP and 4-t-OP in Ialomi?a River water samples collected each month during 2006. The concentration levels of 4-NP and 4-t-OP vary between 0.08–0.17 μg/L with higher values of 0.24–0.37 μg/L in the summer months for 4-NP, and frequently <0.05 μg/L but also between 0.06–0.09 μg/L with higher values of 0.12–0.16 μg/L in July and August for 4-t-OP and were strongly influenced by sesonial and anthropic factors. The method was also applied on samples collected over 2 years 2007 and 2008 from urban wastewaters discharged into sewage or directly into the rivers by economic agents located in 30 Romanian towns. Good results were obtained when the method was used for analysis of effluents discharged into surface waters by 16 municipal wastewater treatment plants, during the year 2008.     

Development and application of microwave assisted extraction (MAE) for the extraction of five polycyclic aromatic hydrocarbons in sediment samples in Johannesburg area, South Africa

A microwave-assisted extraction (MAE) method was verified and applied for the extraction of polycyclic aromatic hydrocarbons (PAHs) in sediment samples. Soxhlet extraction was used as the reference method. The optimum MAE was carried out with 20 mL of hexane/acetone (1:1, v/v) mixture in a 1-g sample at 250 W for 20 min. Soxhlet extraction was carried out with 250 mL of dichloromethane:hexane (1:1, v/v) mixture in a 15-g sample for 24 h in a water bath maintained at 60 °C. The collected extracts were both cleaned up, reduced to 1 mL under nitrogen and then injected into an HPLC fluorescence. To increase the sample throughput, simultaneous MAE was performed. The obtained percentage recoveries ranged from 61 to 93 and 88–98 for MAE and SE, respectively. The optimised MAE method was validated using certified reference material. It was then applied to real sediment samples from in and around the greater Johannesburg area. The sediments from Jukskei River were found to be the most polluted while Hartbeespoort Dam sediments were found to be least polluted. The overall order of concentrations for the studied PAHs per site was as follows: Jukskei River?>?Kempton Park?>?Centurion Dams?>?Natalspruit River (PIT)?>?Hartbeespoort Dam.     

A new nanosilver-based spectrophotometric method for monitoring Eriochrome black T in river water

In this paper, a new spectrophotometric method is reported for the determination of nanomolar levels of Eriochrome black T in environmental samples. The method is based on the catalytic effect of silver nanoparticles on the oxidation of Eriochrome black T by hexacyanoferrate (III) in acetate–acetic acid medium and at 25 °C. The absorbance is measured at 512 nm with the fixed-time method. It relies on the linear relationship between the absorbance difference (?A) and Eriochrome black T amounts in the range of 40–1,250 nM. Under optimum conditions, the sensitivity of the proposed method, i.e., the detection limit corresponding to 80 s, is about 25 nM. The method is featured with good accuracy and reproducibility for Eriochrome black T determination in river water samples without any pre-concentration and separation step.     

Monitoring and measurement of microalgae using the first derivative of absorbance and comparison with chlorophyll extraction method

Monitoring of microalgae in water supplies and industrial applications are becoming increasingly important, yet there are few options available that are simple and accurate, and can provide real-time information. The present work illustrates a new method to determine the concentration of microalgae in water and wastewater using spectrophotometry and the first derivative of absorbance. Chlorella vulgaris was used as an indicator microalga, spiked in water samples representing a range of water qualities (distilled water, surface water, and wastewater), and correlations among C. vulgaris concentrations, absorbance, and the first derivative of absorbance measurements were investigated. In addition, detection limits were established and sensitivity analyses were carried out to determine the lowest C. vulgaris concentrations that can be confidently measured in different water matrices. Finally, the study compared the performance and detection limits of the spectrophotometry-based methods with the well-accepted chlorophyll extraction method. A strong linear relationship (R²?>?0.97) was found between C. vulgaris concentration and absorbance at 695 nm. Using the first derivative of absorbance improved C. vulgaris detection limits by reducing the effects of the background noise and interferences from other substances. The detection limits established using the first derivative method were 0.47, 0.56, and 1.96 mg TVS/L in distilled water, surface water, and wastewater, respectively. In comparison, the detection limits of the chlorophyll extraction method were found to be 19.6, 38.6, and 48.3 mg TVS/L in the same water matrices. These results indicate that first derivative of absorbance can be successfully used for monitoring of microalgae in surface waters and environmental samples as well as in bioreactors used for microalgae cultivation in industrial applications.     

高压液相色谱法测定地表水和饮用水中的阿特拉津

通过条件实验,建立了水体中阿特拉津的高效液相色谱检测法,以ODS C18柱为色谱柱,甲醇:水=60:40为流动相,检测波长225nm,柱温40℃,用二氯甲烷萃取,外标法定量,线性范围为0.02～10.0mg/L,相关系数达0.9999,采样体积为500 ml时,方法检出限为0.012μg/L,精密度在2.5%～11.4...     

Quantification of triazine herbicides in soil by microwave-assisted extraction and high-performance liquid chromatography

A method for the determination of herbicides residues, triazine (atrazine, metribuzin, ametryn, and terbutryn), in soil samples with high-performance liquid chromatography (HPLC)?CUV detection is described. The proposed method is based on microwave-assisted extraction (MAE) of soil samples for 4 min at 80% of 850-W magnetron outputs in the presence of mixture of solvents (methanol/acetonitrile/ethylacetate). Related important factors influencing the MAE efficiency, such as the solvent type and volume, irradiation energy, and time, were optimized in detail. Calibration curve ranges established using HPLC for metribuzin, atrazine, ametryn, and terbutryn are 1.0?C19.0, 0.9?C18.0, 0.6?C11.0, and 0.7?C11.0 µg mL^???1, respectively. The limits of detection of metribuzin, atrazine, ametryn, and terbutryn are 0.30, 0.24, 0.16, and 0.20 µg mL^???1 while limits of quantification are 1.0, 0.80, 0.50, and 0.60 µg mL^???1, respectively. A Plackett?CBurman factorial design was used as a screening method in order to select the variables that influence MAE extraction. The recoveries of the method at three different spiked levels were assessed by analyzing real soil samples and were found to be in the range of 83.33 ± 0.12?C96.33 ± 0.23 with good precision (<8%).     

Determination of trace transition metals in environmental matrices by chelation ion chromatography

Trace transition metals (Fe^3?+?, Mn, Cu, Cd, Co, Zn, Ni) in environmental samples were analyzed by chelation ion chromatography using a mixed bed ion-exchange column with pyridine-2,6-dicarboxylic acid (PDCA) and oxalic acid as eluent and large volume direct injection (1,000 ??l). The two eluents, PDCA and oxalic acid, were tested, and repeatability and detection limits were compared. The total analysis time was ~15 min. The separation with PDCA was more successful than that obtained with acid oxalic. It was observed that utilizing PDCA resulted in lower detection limits, higher repeatability, and a quantitative detection of Cd and Mn, which coelute as a single peak when using the oxalic acid. At last, the PDCA calibration graphs resulted linear (r ²?>?0.999) in the range 0.4?C1,000 ??g/L. The procedure was applied to the analysis of metals in soils and in water samples. The results obtained from the analysis of natural waters have demonstrated that the method is simple and efficient, therefore, can be used for the determination of metals in natural waters using a continuous and automatic monitoring system.     

Quantification of PAHs and chlorinated compounds by novel solid-phase microextraction based on the arrays of tin oxide nanorods

The results of an innovative study on a new and highly efficient stationary phase based on the SnO₂ nanorods coating on fused silica have been reported in this paper. SnO₂ nanorods have been grown on fused silica fibers using a hydrothermal process. The extraction properties of the fiber were investigated using headspace solid-phase microextraction (HS-SPME) mode coupled with gas chromatography–mass spectrometry detection for 1,4-dichloro-2-nitrobenzene, biphenyl, and acenaphthene. The effect of different variables on extraction efficiency was studied simultaneously using Box–Behnken method as experimental design. The variables of interest in the HS-SPME were salt effect, adsorption temperature, extraction, and desorption time. Under optimal conditions, the calibration curves were linear up to 10²–10⁵ ng?L^?1 (R ²?>?0.998) with detection limits of 10^?3, 10^?1, and 10 ng?L^?1 for acenaphthene, biphenyl, and 1,4-dichloro-2-nitrobenzene, respectively. The relative standard deviations for single fiber and fiber to fiber were less than 9.8 and 12.5 %, respectively. The high stability of the SnO₂ nanostructure coating is proved at relatively high temperatures (up to 300 °C) with a high extraction capacity and long lifespan (more than 100 times). By applying the proposed technique, promising recoveries (93–98 %) were obtained in the analysis of environmental water samples.     

A nanosilver-based spectrophotometric method for determination of malachite green in surface water samples

A new spectrophotometric method is reported for the determination of nanomolar level of malachite green in surface water samples. The method is based on the catalytic effect of silver nanoparticles on the oxidation of malachite green by hexacyanoferrate (III) in acetate–acetic acid medium. The absorbance is measured at 610 nm with the fixed-time method. Under the optimum conditions, the linear range was 8.0?×?10^?9–2.0?×?10^?7?mol?L^?1 malachite green with a correlation coefficient of 0.996. The limit of detection (S/N?=?3) was 2.0?×?10^?9?mol?L^?1. Relative standard deviation for ten replicate determinations of 1.0?×?10^?8?mol?L^?1 malachite green was 1.86 %. The method is featured with good accuracy and reproducibility for malachite green determination in surface water samples without any pre-concentration and separation step.     

Sediment load and bioconcentration of heavy metals by shrimp (Peaneus notalis) from Epe Lagoon, Nigeria

In many developing countries, surface waters, especially rivers and lagoons, have become deposition sites for all sorts of wastes. Three sampling sites located trigonally on Epe lagoon, Lagos, Nigeria were identified, and water, sediment, and commonly farmed shrimp, Peaneus notalis, were sampled and assessed for heavy metal concentrations. Zn, Pb, Ni, Cu, Cr, Cd, and Mn were determined in the aqua regia digests of the samples by means of Perkin Elmer AAnalyst 200 atomic absorption spectrophotometer. Heavy metals occurred above detection limits at all sites. The highest load of these trace elements was found in sediment samples followed by the water samples. The levels observed in the shrimp samples, however, were much lower than WHO levels. In the distribution, zinc was the highest metal found in the samples ranging from 17.94 ± 2.60 mg/L in water to 37.85 ± 9.35 μg/g in sediments. The least was Cd 0.03 ± 0.01 mg/L in water and 0.28 ± 0.04 μg/g in sediments. Lead was the most widely varied metal in shrimp with a 84.38% coefficient of variation. Apart from Cr, the metals appeared to be fairly and evenly distributed in the sediment, with coefficient of variation ranging from 14.29% (Cd) to 24.76% (Mn) The variations were between 14.49% (Zn) and 66.67% (Cr) in the water samples. The paired t test carried out between water and sediment, water and shrimp, and shrimp and sediment was significant at p?=?0.05. Three-factor analysis of variance did not reveal any significant difference in metal burdens among the trigonally located sites under investigation. Shrimp samples showed evidence of bioaccumulation but are still below internationally established levels.     

Dissipation pattern and pre-harvest residue limit of abamectin in perilla leaves

The pre-harvest residue limit (PHRL) of abamectin (abamectin B1a and B1b) in Perilla frutescens leaves grown under greenhouse conditions were investigated using high-performance liquid chromatography with a fluorescence detector. Samples were extracted with acetonitrile. The extract was purified through a solid phase extraction procedure. Then the purified extract was derivatized with trifluoroacetic anhydride and N-methylimidazole to form a strong stable fluorescent derivative of abamectin. Finally, derivatized abamectins were conveyed to the detector via an Atlantis C₁₈ column, with water and methanol as a mobile phase. Calibration curves were linear over the calibration ranges with coefficients of determinants r ²?≥?0.999. The limits of detection and quantification were 0.0033 and 0.01 mg kg^?1 for abamectin B_1a and B_1b, respectively. Recovery was assessed in a control matrix at two different fortification concentrations, with three replicates for each concentration. Good recoveries were obtained for the target analytes and ranged from 82.11 to 93.03 %, with relative standard deviations of less than 8 %. The rate of disappearance of total abamectin on perilla leaves for recommended and double the recommended doses was described as first-order kinetics with a half-life of 0.7 days. Using the PHRL curve, we could predict the residue level of total abamectin to be 0.92 mg kg^?1 at 7 days before harvest or 0.26 mg kg^?1 at 4 days before harvest, which would be below the provisional MRL designed by the Korea Food and Drug Administration.     

Liquid chromatography-hydride generation-atomic absorption spectrometry for the speciation of tin in seafoods

Liquid chromatography with hydride generation atomic absorption spectrometry as the detection system was applied to the separation and determination of inorganic tin, tributyltin, dibutyltin, monobutyltin, diphenyltin and monophenyltin. A reversed phase C18 column and a methanol/water/acetic acid (70:27:3, v/v/v) mixture containing 0.05%(v/v) triethylamine and 0.1%(w/v) tropolone as the mobile phase (isocratic elution) were used. Extraction of organotins from the samples was carried out using methanol containing 0.05%(w/v) tropolone, a process that was repeated twice. The supernatants were shaken with water and dichloromethane in a separating funnel and the organic phase was collected and evaporated to dryness. When the method was applied to the speciation of tin in fresh and canned mussels, no organotins above the detection limits were identified in any of the samples, inorganic tin being the only species detected. The reliability of the procedure was checked by analyzing the total tin content of the samples by electrothermal atomic absorption spectrometry and by speciation of tin in a certified reference material, mussel tissue (CRM 477). The method can be used for environmental monitoring of organotins contaminated samples.     

Multi-component analysis of polar water pollutants using sequential solid-phase extraction followed by LC-ESI-MS

A multi-component screening analysis method for polar to medium-polar water pollutants was developed. Sample clean-up and group separation are performed by sequential solid-phase extraction (SSPE) using automated SPE with C18 and polymeric sorbent materials. Analyses are performed by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) using a single-quadrupole instrument. More than 90 priority compounds of environmental interest--comprising the most important chemical and substance classes: phenols, carboxylic acids, aromatic sulfonates, aromatic amines, pharmaceuticals, surfactants, dyes, and pesticides--have been chosen for the experiments. The compounds are divided by the SSPE procedure into 3 different polarity classes. The extraction recoveries were determined in the 3 fractions for every single substance, and were for most of the analytes in the range of 50-100%. A mixture of hexane-dichloromethane was used for the elution of nonpolar compounds like alkylphenols from C18. Methanol and acetone are well suited for the elution of more polar substances. The limits of detection (LODs) were determined for all compounds. Effluents from municipal and industrial wastewater treatment plants (WWTPs) treating waste water from textile industries; and the corresponding receiving waters (rivers and lakes) have been analysed with the developed method. Urban and industrial pollution was observed in rivers and streams in the area north of Milan, Italy. In the water samples different phenols (nitrophenols, bisphenol A, nonylphenol), alkylphenol ethoxylate surfactants, their metabolites with endocrine disrupting potential, aromatic sulfonates, linear alkylbenzenesulfonate surfactants, dyes, pesticides, pharmaceuticals, and a dichlorobenzidine compound were identified.     

A simple extraction procedure for determination of total mercury in crude oil

The determination of mercury in crude oil and petroleum products is particularly difficult due to the volatile nature of both mercury and the matrix, which may lead to significant loss of the analyte. A simple extraction method for total mercury has been developed to determine total mercury in crude oil using cold vapor atomic fluorescence spectrometry. The homogenized crude oil sample was diluted to 5, 10, and 20 % (w/w) in toluene. The diluted crude oil samples were spiked with 10 and 40 μg/kg (w/w). The samples were extracted using an oxidant/acid solution, BrCl/HCl. The mercury was extracted into the aqueous phase; the ionic mercury was then reduced to volatile elemental mercury (Hg⁰) by stannous chloride (SnCl₂). The mercury vapor was detected by Merlin cold vapor atomic fluorescence spectrometry at a 253.7-nm wavelength. The average recoveries for mercury in spiked diluted crude oil (10 and 40 μg/kg, w/w) were between 96 and 103 %, respectively, in 5 and 10 % spiked diluted crude oil. Whereas, low recoveries (<50 %) were recorded in 20 % diluted spiked crude oil. The method detection limit was calculated as t _{(0.01)(n ? 1)}?×?SD where t is the student's value for 99 % confidence level and standard deviation estimate with n???1 degrees of freedom. The method detection limit was found to be 0.38 μg/kg based on 5 g of diluted crude oil sample. The method is sensitive enough to determine low levels of mercury in crude oil.     

Solid-phase extraction of Mn(II) and slurry analysis of the sorbent by electrothermal atomic absorption spectrometry

In this study, a challenging preconcentration/separation method based on the sorption of manganese on ethylene glycol dimethacrylatemethacrylic acid copolymer (EGDMA-MA) treated with ammonium pyrrolidine dithiocarbamate (APDC) and its slurry analysis by electrothermal atomic absorption spectrometry was described. Optimum conditions for quantitative sorption, as well as for preparing a homogeneous and stable slurry were investigated. A 100-fold enrichment factor could be reached. The analyte element in certified sea-water and bovine-liver samples were determined in the range of 95% confidence level. The proposed technique is fast, simple, and the risk of contamination is low. The limit of detection of the method for manganese in the slurry of the blank subjected to the proposed procedure was 0.07 μg L^?1 (3δ, N:10) corresponding to 0.56 μg kg^?1 slurry.     

Quantitative detection of nitrate in water and wastewater by surface-enhanced Raman spectroscopy

The presence of inorganic nitrogen species in water can be unsuitable for drinking and detrimental to the environment. In this study, a surface-enhanced Raman spectroscopy (SERS) method coupled with a commercially available gold nanosubstrate (a gold-coated silicon material) was evaluated for the detection of nitrate and nitrite in water and wastewater. Applications of SERS coupled with gold nanosubstrates resulted in an enhancement of Raman signals by a factor of ～10⁴ compared to that from Raman spectroscopy. The new method was able to detect nitrate with linear ranges of 1–10,000 mg NO₃ ^?/L (R ²?=?0.978) and 1–100 mg NO₃ ^?/L (R ²?=?0.919) for water and wastewater samples, respectively. Among the common anions, phosphate appeared to be the major interfering anion affecting nitrate measurement. Nevertheless, the percentage error of nitrate measurement in wastewater by the proposed SERS method was comparable to that by ion chromatography. The nitrate detection limits in water and wastewater samples were about 0.5 mg/L. The SERS method could simultaneously detect sulfate, which may serve as a reference standard in water. These results suggested that the SERS coupled with nanosubstrates is a promising method to determine nitrate concentrations in water and wastewater.     

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.     

Quantification of ultra-trace amounts of copper by using off-line solid phase extraction-flame atomic absorption spectrometric determination through the octadecyl silica-bonded phase membrane (OSPM) C18 disks impregnated with 2,2'-[ethane-1,2-diylbis(thio)]dianiline

This study reports a very selective, easy, and precise method for rapid separation of trace amounts of copper in aqueous samples using octadecyl silica-bonded phase membrane disks modified by 2,2'-[ethane-1,2-diylbis(thio)]dianiline (EDTD) combined with flame atomic absorption spectrometric determination. In addition, the synthesis and spectral characterization of EDTD have been described in detail. All the affecting experimental variables such as pH, amount of modifier, eluent type, sample and eluent flow rate, interfering ions, and disk capacity were also investigated. The target analyte (trace copper) was quantitatively retained at pH?=?4 and eluted with 6.0 mL of 0.5 M HNO₃ at flow rates of 40 and 10 mL min^?1 for analyte passage and elution steps, respectively, through the disks modified with 17.0 mg of EDTD. The proposed method also allows an enrichment factor of about 500 and has a detection limit of 0.005 ng mL^?1. The method has been successfully applied for isolation and determination of copper in different water samples, peppers, and standard alloys.     

液液萃取-高效液相色谱法测定水中四乙基铅

采用高效液相色谱紫外检测器测定水中四乙基铅,用二氯甲烷液液萃取,以甲醇/水混合溶液(体积比为95:5)为流动相,Z0RBAX Eclipse XDB-C18色谱柱分离,选择测定波长为280 nm.方法在0.100mg/L～1.00mg/L范围内线性良好,检出限和测定下限分别为0.01μg/L和0.04μg/L,水样平行...