Effervescence assisted dispersive liquid–liquid microextraction followed by microvolume UV-Vis spectrophotometric determination of surfactants in water

The novel and simple methods for the sensitive determination of cationic and anionic surfactants in water based on effervescence assisted dispersive liquid–liquid microextraction and microvolume UV-Vis spectrophotometry have been developed. The method involves ion-pair extraction of cationic and anionic surfactants with organic dyes (methyl orange and azure A, respectively) during the dispersion of extraction solvent (CHCl₃) by CO₂ bubbles which are formed by the injection of a mixture of the extraction solvent and proton donor solvent into the sample solution which contains carbonate-ions as effervescency agent. The analytical performance of the proposed procedure was compared with the conventional dispersive liquid–liquid microextraction. Appropriate experimental conditions for both methods were investigated. The absorbances of the colored extracts at wavelengths of 440 and 625 nm obey Beer's law within the range of 0.1–5.0 mg/L for both cationic and anionic surfactants. The limit of detection (LOD) obtained using the effervescence assisted extraction method was 30 µg/L for cationic and anionic surfactants. The proposed methods were successfully applied to determination of surfactants in water samples.     

A sensitive method for selective determination of vanadium species by dispersive liquid–liquid microextraction (DLLME) with spectrophotometric detection

A simple, fast, and low-cost analytical procedure was developed for trace-level determination of inorganic vanadium species by dispersive liquid–liquid microextraction in combination with spectrophotometry. Vanadium in pentavalent form, V(V), was quantitatively extracted into organic phase as 4-(2-pyridylazo)-recorcinol (PAR) complex in the presence of N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB) as counter-ion. Vanadium (IV) was masked with 1,2-diaminocyclohexanetetraacetic acid to allow speciation analysis. Total vanadium was determined after oxidation of V(IV) to V(V). The main factors affecting preconcentration and spectrophotometric detection of vanadium species such as pH, concentration of PAR and CTAB, the type and volume of the extraction, and disperser solvents were optimized. The limit of detection and enhancement factor obtained under optimum conditions were found to be 0.06 μg L^?1 and 98, respectively. Relative standard deviations for V(IV) and V(V) at 3.0 μg L^?1 were less than 2.4%. The presented procedure was applied to environmental water samples for selective determination of vanadium species. Moreover, the method was applied to determination of vanadium in edible salt samples, due to its applicability in high-NaCl-containing solutions. The validity of proposed method was proven by spike recovery experiments and also independent analysis by inductively coupled plasma mass spectrometry.     

Fast dispersive liquid–liquid microextraction of pesticides in water based on a thermo-switchable deep eutectic solvent

Environmental Chemistry Letters - Accurate measurements of pesticide levels in the environment are necessary to set policies, yet actual analytical methods are limited by the use of toxic solvents...     

Dispersive liquid–liquid microextraction of cadmium(II) for preconcentration prior to flame atomic absorption spectrometric detection in water

A dispersive liquid–liquid microextraction procedure for cadmium(II) as its 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol chelate is presented. Carbon tetrachloride and methanol were used as extraction and dispersive solvents, respectively. After phase separation, the preconcentrated-separated cadmium(II) is determined by flame atomic absorption spectrometry with a microinjection technique. The factors which affected the extraction efficiency, i.e. the pH of the sample solution and the volumes of reagent and sample were investigated. The effects of some alkali, alkali earth, and transition metal ions, and of some anions on the recovery of cadmium were also studied. A preconcentration factor of 250 was obtained for a sample volume of 50?mL under optimum conditions. The method was validated by analysis of certified reference materials and applied to some water samples from Turkey.     

Determination of carazolol in pharmaceutical formulations by gas‐liquid‐chromatography (GLC)

A gas‐liquid‐chromatographic procedure for the quantitative determination of authentic carazolol and carazolol in tablets (Conducton^(R)?) has been described. Carazolol in tablets was extracted with absolute alcohol before injecting onto the gas Chromatograph. The concentration range adopted varied between 0.2 mg to 1.0 mg/ml of carazolol in alcohol solution. The results obtained were 97.6%±3.2 and 98.4%±2.6 for the stated and added amounts respectively.     

Characterisation of cobalt‐binding proteins in occupational cobalt exposuret†

In animal experimentations cobalt is found to be carcinogenic under conditions which are comparable with a possible exposure of human beings at the workplace.^1,2 Little is known about binding and distribution of incorporated cobalt in blood.

Blood, serum and plasma of workers occupationally exposed to cobalt were analyzed concerning cobalt‐binding. The samples were focused by preparative IEF in layers of granulated gels. The cobalt concentrations in the isolated fractions were measured with the aid of flameless atomic absorption spectrometry. The whole blood samples exhibit peaks with different sizes in the pH‐5‐ and ‐7‐range. The proportion of these peaks can change with individual samples. In serum and plasma cobalt is found only in the pH‐5‐range.

When separated by gelelectrophoresis under denaturating conditions the cobalt‐fractions in all blood, serum and plasma samples shows a similar protein pattern. Several proteins with different molecular weights are detected in the pH‐5‐fractions, whereas only hemoglobin is found in the pH‐7‐fractions. In agreement with these results is the refocusing in ultrathin‐layer of polyacrylamide. Heterogeneous protein patterns are demonstrated with the pH‐5‐fractions; the pH‐7‐fractions yield only the hemoglobin pattern.

In vivo cobalt is bound to plasma proteins‐perhaps‐albumin^3,4‐and hemoglobin. Till now the chemical structure of the binding is unknown.     

Rapid liquid–liquid extraction for the reliable GC/MS analysis of volatile priority pollutants

Mass spectrometry is a powerful tool for the analysis of organic pollutants in the environment. Nevertheless, sample preparation for GC/MS analysis is often criticized for being too laborious and requiring expensive equipment. Thus, purge-and-trap or headspace devices are the most popular nowadays to investigate volatile organic pollutants. At the same time, modern commercial high-resolution mass spectrometers allow for the significant simplification of the sample preparation procedures due to better acquisition rate, accurate mass measurements, and improved sensitivity. Here, we used a time-of-flight high-resolution mass spectrometer Pegasus GC-HRT (LECO, USA) to identify and quantify 47 volatile priority organic pollutants in water. The developed accelerated water sample preparation approach requires just 1 mL of water and 1 mL of dichloromethane. The detection limits of the analytes are about 1 μg L^?1, while the quantification limits are approximately 5 μg L^?1. These limits correspond to those required by Method 8260C of the United States Environmental Protection Agency. Here, we demonstrate that sample preparation for the reliable and sensitive GC/MS analysis of volatile organic priority pollutants may be achieved in 5 min in 5-mL vials in the field or just prior to GC/MS analysis in the laboratory without the use of any expensive equipment.     

The estimation of bioconcentration factors of aromatic hydrocarbons by high‐performance liquid chromatography

The determination of Bioconcentration Factors (BCF) via HPLC capacity factors (k') has been studied, including the effect of column type and mobile phase composition on the correlation between log BCF and log k’. Values of BCF correlate well with the phenylsilica column capacity factors. The phenylsilica column followed by C18 column give better correlations than either C8 or C2 column. The use of HPLC with phenylsilica as stationary phase and methanol‐water as mobile phase in the prediction of BCF can be at least as good or better than the use of n‐octanol/water partitioning system. There are no significant differences in the correlations between log k’ and log BCF with the changes of methanol concentration in the mobile phase, and it seems that a high proportion of methanol in the eluent is required to obtain good results.     

Determination of 1‐octanol/water partition coefficients of isocyanate compounds by an HPLC method

The octanol/water partition coefficients (P _ow) of six monoisocyanate and five diisocyanate compounds were determined by high performance liquid chromatograph (HPLC) methods. Two HPLC peaks, a broad tailed peak followed by a sharp one, were observed with all compounds. The later peak was identified as the isocyanate compound. The P _ow value for each isocyanate compound was determined by fitting the capacity factor of the peak to the regression equation drawn from those of reference compounds. The hydrophobic substituent constants for the isocyanate group were calculated with each of the compounds. The value of this constant was strongly dependent on the type of carbon bound to the isocyanate group and the average values for the aromatic and aliphatic isocyanate groups were 0.35 and — 0.52, respectively. Because of the reactivity of those compounds in the aquatic environment, the P _ow has little relevance to calculation of their environmental fate and ecotoxicity.     

Detection of organic contamination in sediments by double-shoot pyrolysis–GC/MS

Pyrolysis coupled with gas chromatography–mass spectrometry (Py–GC–MS) has been previously proved to be an appropriate tool for the screening of organic contaminants in sediments. In this work the double-shoot pyrolysis technique has been applied to assess the contamination degree of sediment samples from Castro Marim Natural Park (South Portugal) and the Ria of Huelva (SW Spain). Compounds released both by thermodesorption at sub-pyrolysis temperatures (250–280°C) and subsequent pyrolysis (300–500°C) revealed information on the origin of the sedimentary organic matter and the occurrence of organic contamination in the sediments. Thermal desorption was found to be effective in releasing organic contaminants from spiked samples. However, in real sediments samples, higher pyrolysis temperatures (>300°C) were necessary to detect the occurrence of organic contaminants. Particularly polycyclic aromatic hydrocarbons (PAHs) and linear alkylbenzenes (LABs) were detected in variable proportions in most sediment samples.     

Determination of the framework conditions and research–development needs for the dissemination of cleaner (sustainable) production applications in Turkey

SUMMARY

A cross-section survey of five states in Nigeria was derived through a stratified random sampling technique in 1999–2000 to assess the contribution of traditional knowledge in environmental conservation. Data were collected through a combination of questionnaire survey and discussions with stakeholders, with field assessment of herb gardens. Interviews were held with 1953 respondents composed of women, men and youths drawn from 20 settlements in 10 local government areas in the savanna and rainforest ecological zones.

The results derived from data analysis indicated that: (i) the rural communities were willing to accept integrated rural land-use practices that would conserve species and habitats, sustain the rural economy and the socio-cultural lifestyles of the people; (ii) the people at the local level had some basic knowledge about species and habitats, and have been conserving the forests with traditional land tenure rights; and (iii) environmental projects acceptable to the rural communities must be beneficial to the people, participatory, integrated with traditional knowledge and based on local needs.     

Generation of new carbon–carbon and carbon–heteroatom bonds mediated by agro-waste extracts: a review

Agro-waste extracts are considered green solvents since they are easy to handle, readily accessible from natural waste feedstock, biodegradable and recyclable. Therefore, the employment of these extracts in reaction media has emerged as the most useful and eco-friendly alternative in modern organic chemistry. Here, we review recent developments for the generation of new carbon–carbon and carbon–heteroatom bonds mediated by agro-waste extracts. We show that these aqueous extracts have great applicability in several transformations, including condensations, oxidations, multicomponent and coupling reactions. The challenges and advantages on the use of water of agro-waste extracts in synthetic methodologies is also detail.

     

Analyses of phenolic compounds occurring in olive oil mill wastewaters by GC–MS

Phenolic compounds in olive oil mill wastewaters were analysed by HRGC–MS after extracting the acidified solution with ethyl acetate and derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide. Both simple and complex phenols were detected with the latter being the most abundant. 1,2-dihydroxybenzene (catechol), p-hydroxyphenyl ethanol (tyrosol), 3,4-dihydroxyphenyl ethanol (hydroxytyrosol) and 4-hydroxy-3-methoxyphenyl ethanol (homovanillyl alcohol) predominated among the simple phenols using a gas chromatograph coupled with a mass selective detector.     

Cytotoxic study in the treatment of tetracycline by using magnetic Fe3O4–PAMAM–antibody complexes

Environmental Chemistry Letters - Antibiotics are widely used as drugs to treat human and animal diseases. However, the widespread use of antibiotics has induced environmental...     

Endeavors on the development of efficient and sustainable supported metal catalysts for chemical synthesis on solid–liquid interfaces

Supported metal catalysts, particularly for precious metals, have gained increasing attention in green synthetic chemistry. They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue, as well as reusability of the high-cost catalysts. Although great effort has been spent, the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable r...     

Combined sorptional–photocatalytic remediation of dyes by polyaniline Zr(IV) selenotungstophosphate nanocomposite

A polyaniline Zr(IV) selenotungstophosphate nanocomposite was prepared via sol-gel method and characterized by thermogravimetric analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, and transmission electron microscopy. The combined sorptional–photocatalytic activity of the nanocomposite for degradation of methylene blue and malachite green was investigated and was found to be more efficient than separate adsorption in the dark followed by photocatalysis. The dyes were degraded in 3 h by 96% and 89% by the combined process, as compared to 86% and 72% by the two-step process in 5 h. The nanocomposite material showed antimicrobial activity against Staphylococcus aureus and Escherichia coli.     

Adsorptive removal of direct dyes by PEI-treated peanut husk biomass: Box–Behnken experimental design

This paper reports the application of Box-Behnken experimental design to illustrate the adsorption of direct dyes (Indosol Black NF and Indosol Orange RSN) using polyethyleneimine (PEI)-treated peanut husk biomass. The effect of three independent variables (initial dyes concentration, biosorbent dose and pH) was investigated during the study. Maximum biosorption capacity (141 and 98.2 mg/g) of PEI-pretreated biomass was achieved with 200 mg/L initial dye concentration and 0.05 g/50 mL biomass dose for Indosol Black NF and Indosol Orange RSN, respectively. Acidic pH was found to be favourable for maximum dyes removal. Characterisation of biosorbent was carried out through Fourier transform-infrared spectroscopy (FT-IR), scanning electron microscopy, thermogravimetric analysis (TGA) and point of zero charge determination. FT-IR analyses confirmed the involvement of carboxylic and carbonyl groups. The desorption study was also conducted to check out the possibility of regeneration of dyes and adsorbent and it was found that 51.58 and 76.6% of Indosol Black NF and Indosol Orange RSN, respectively, can be desorbed from the loaded biosorbent by using 1 M NaOH solution. The results indicated that PEI-treated peanut husk biomass can be used as an efficient biosorbent for the removal of Indosol Black NF and Indosol Orange RSN dyes from aqueous solutions.     

Characterisation and classification of hoarfrost samples collected in Poland (2003–2005) by discriminant analysis

Discharges of nutrients, urea, dissolved organic matter and heavy metals by a sewage underwater pipeline are analysed in comparison to environmental conditions in a shallow coastal zone. Variable thermo-haline stratifications of the water column and currents in upper (2.62–34.97 cm s^?1) and deeper (0.83–10.91 cm s^?1) layers drive vertical diffusion and lateral transport of wastewaters. Loads of reactive phosphorus (0.13 tons d^?1) and ammonium (1.62 tons d^?1) by the pipeline are not negligible compared to the major river loads in the gulf. High concentrations of urea (≤11.51 μmol N dm^?3) were found in the area of wastewater release. Ammonium uptake (6.14–534 nmol N dm^?3 h^?1) strongly exceeded nitrate uptake (0.19–138 nmol N dm^?3 h^?1), indicating that discharges of ammonium by the pipeline are actively assimilated by plankton community even at low levels of light. Distribution of Zn (≤27.7 ppb), Cu (≤25.6 ppb), Cd (≤0.80 ppb) and Pb (≤13.5 ppb) in the water column and the measurement of their complex-forming capacity in seawater did not indicate a persistent perturbation of the pelagic environment due to heavy metals.