Determination of organophosphorus fire retardants and plasticizers in wastewater samples using MAE-SPME with GC-ICPMS and GC-TOFMS detection

Determination of organophosphorus fire retardants and plasticizers at trace levels in wastewater is described. In this work, microwave assisted extraction (MAE) and solid-phase microextraction (SPME) are used for sample preparation to extract and preconcentrate the analytes, followed by analysis by gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS) for phosphorus-specific detection. Gas chromatography coupled to time of flight mass spectrometry (GC-TOF-MS) was used to confirm the organphosphorus fire retardants in wastewater. The detection limits of organophosphorus fire retardants (OPFRs) were 29 ng L(-1) for tri-n-butyl phosphate (TnBP), 45 ng for L(-1) for tris(2-butoxyethyl)phosphate (TBEP), and 50 ng L(-1) for tris(2-ethylhexyl)phosphate (TEHP). Optimized extraction conditions were performed at 65 degrees C for 30 min and with 10% NaCl. Application of MAE during the sample preparation prior to the SPME allowed the detection of tris(2-ethylhexyl) phosphate, which has been difficult to determine in previous work. Application of the method to wastewater samples resulted in detecting 3.1 microg L(-1) P from TnBP, 5.0 microg L(-1) P from TBEP, and 4.0 microg L(-1) P from TEHP. The presence of these compounds were also confirmed by SPME-GC-TOF-MS.     

Distribution, correlation, and source apportionment of selected metals in tannery effluents, related soils, and groundwater—a case study from Multan, Pakistan

The short-term responses of H₂O₂-depletion-related parameters in moss Hypnum plumaeforme to the combined stress induced by Pb and Ni were investigated. The results showed that the Pb and Ni stress induced dose-dependent accumulation of hydrogen peroxide (H₂O₂). The increase of peroxidase (POD) activity and decrease of ascorbate peroxidase (APX) activity were observed under the combined heavy metal application. The antioxidants, ascorbate (AsA) and proline content, increased significantly when the metals were applied together. The study indicated that the cell damage caused by Pb stress was higher than that caused by Ni stress, Pb and Ni had synergistic effect in inducing the oxidative stress in moss H. plumaeforme, especially under the combination of high concentration of Ni (0.1 and 1.0 mM) and Pb. Content of proline, H₂O₂ and the activity of POD, all showed a dose-dependent increase under Pb and Ni stress, suggesting their practical value as biomarkers in moss biomonitoring, especially in the case of light pollution caused by heavy metals without the changes in the appearance of mosses.     

Design and Characterization of PVA–Methacrylic Acid Based Smart Polymeric System for Controlled Release of Metoprolol

In the present work covalently crosslinked smart polymeric system of hydrogel based on poly vinyl alcohol (PVA) and methacrylic acid (MA) was designed by free radical polymerization with different compositions using glyoxal (40 % water solution) as crosslinker. It was observed that swelling of hydrogel had a pronounced enhancing effect on increasing the concentration of MA due to availability of more ionized carboxylic groups of MA but produced an opposite effect on increasing the concentration of glyoxal owing to less porous structure. As far as PVA is concerned, swelling did not show significant effect on increasing the concentration of PVA. Hydrophilic polymer PVA rich in hydroxyl group pertained to be highly interactive with water. It was examined that the release of metoprolol tartrate decreased with increased concentration of glyoxal, but increased with increase in concentration of MA. PVA/MA hydrogel was characterized by Fourier transform infrared spectroscopy and X-ray diffraction to study the structure and crystallinity of hydrogel respectively. Morphology was studied through scanning electron microscopy. Furthermore differential scanning calorimetry and thermogravimetric analysis were also performed to characterize thermal stability. It may be concluded that the mechanism of drug release was mainly non-Fickian diffusion.     

The invasion paradox: reconciling pattern and process in species invasions

The invasion paradox describes the co-occurrence of independent lines of support for both a negative and a positive relationship between native biodiversity and the invasions of exotic species. The paradox leaves the implications of native-exotic species richness relationships open to debate: Are rich native communities more or less susceptible to invasion by exotic species? We reviewed the considerable observational, experimental, and theoretical evidence describing the paradox and sought generalizations concerning where and why the paradox occurs, its implications for community ecology and assembly processes, and its relevance for restoration, management, and policy associated with species invasions. The crux of the paradox concerns positive associations between native and exotic species richness at broad spatial scales, and negative associations at fine scales, especially in experiments in which diversity was directly manipulated. We identified eight processes that can generate either negative or positive native-exotic richness relationships, but none can generate both. As all eight processes have been shown to be important in some systems, a simple general theory of the paradox, and thus of the relationship between diversity and invasibility, is probably unrealistic. Nonetheless, we outline several key issues that help resolve the paradox, discuss the difficult juxtaposition of experimental and observational data (which often ask subtly different questions), and identify important themes for additional study. We conclude that natively rich ecosystems are likely to be hotspots for exotic species, but that reduction of local species richness can further accelerate the invasion of these and other vulnerable habitats.     

Statistical evaluation of hydrobiological parameters of Narmada River water at Hoshangabad City, India

Narmada is considered to be the lifeline of the state of Madhya Pradesh in Central India. The Narmada water is used for bathing, drinking, irrigation and industrial purposes. The city sewage and industrial effluent from Security paper mill at Hoshangabad drains in the Narmada River and pollutes the water quality. Urban sewage enters into Narmada through main nallas. River water quality at Hoshangabad has become a matter of concern due to continuous changing environment and increasing social and industrial activity that influence the water quality directly or indirectly. The present investigation is undertaken to study the effect of domestic sewage and effluent from Security paper Mill on the water quality and ecology of river Narmada at Hoshangabad. The study is carried on at four sites along with the bank of river Narmada. Water samples from four stations were collected, out of which three main sewage mixing points of the city and one fresh water site are taken into account. The samples collected were analyzed, as per standard methods parameters such as Temperature, pH, were measured in-situ. The statistical evaluations were also made. The result showed increase in BOD, Nitrates, Phosphates and Total Coliforms, No. of phytoplanktons. The results revealed that most of the water samples were below or out of limited; according to the WHO, BIS standards.     

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

Characterization, Source Identification and Apportionment of Selected Metals in TSP in an Urban Atmosphere

To understand the metal distribution characteristics in the atmosphere of urban Islamabad, total suspended particulate (TSP) samples were collected on daily 12 h basis, at Quaid-i-Azam University campus, using high volume sampler. The TSP samples were treated with HNO₃/HClO₄ based wet digestion method for the quantification of eight selected metals; Fe, Zn, Pb, Mn, Cr, Co, Ni and Cd by FAAS method. The monitoring period ran from June 2001 to January 2002, with a total of 194 samples collected on cellulose filters. Effects of different meteorological conditions such as temperature, relative humidity, wind speed and wind direction on selected metal levels were interpreted by means of multivariate statistical approach. Enhanced metal levels for Fe (930 ng/m³), Zn (542 ng/m³) and Pb (210 ng/m³) were found on the mean scale while Mn, Cr, Co and Ni emerged as minor contributors. Statistical correlation study was also conducted and a strong correlation was observed between Pb-Cr (r=0.611). The relative humidity showed some significant influence on atmospheric metal distribution while other meteorological parameters showed weak relationship with TSP metal levels. Regarding the origin of sources of heavy metals in TSP, the statistical procedure identified three source profiles; automobile emissions, industrial/metallurgical units, and natural soil dust. The metal levels were also compared with those reported for other parts of the world which showed that the metal levels in urban atmosphere of Islamabad are in exceedence than those of European industrial and urban sites while comparable with some Asian sites.     

Alumina-supported oxime for the degradation of sarin and diethylchlorophosphate

1-(4-Chlorophenyl))-N-hydroxymethanimine and cyclohexyl-N-hydroxymethanimine were synthesized and a well-established oxime, i.e., 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride was purchased. Thereafter; all were loaded over Al₂O₃ using incipient wetness technique. The prepared systems were characterized using surface area analyzer, scanning electron microscope, energy dispersive X-ray spectrophotometer, Fourier transform infrared spectrophotometer and thermogravimetric analyzer. Kinetics of the degradation of sarin (GB) and simulant, i.e. diethylchlorophosphate (DEClP) was studied over synthesized oxime impregnated Al₂O₃ and results were compared with well reported oxime impregnated Al₂O₃. Kinetics of reaction was found to be following the pseudo first order reaction kinetics. The order of reactivity of the prepared systems was found to be cyclohexyl-N-hydroxymethanimine/Al₂O₃ > 1-(4-chlorophenyl)-N-hydroxymethanimine/Al₂O₃ > 2-[(hydroxyimino)methyl]-1-methylpyridinium chloride/Al₂O₃ > Al₂O₃. From the reaction kinetics it was observed that the reaction with DEClP was faster than with GB. Cyclohexyl-N-hydroxymethanimine/Al₂O₃ was found to be the most reactive system with half-life of 0.94 and 15 h for DEClP and GB respectively.     

Total dissolved and bioavailable elements in water and sediment samples and their accumulation in Oreochromis mossambicus of polluted Manchar Lake

The concentrations of 15 elements were determined in water, sediment and tissues of fish (Oreochromis mossambicus) collected from five sampling stations of Manchar Lake in 2005 for two successive seasons, winter (WS) and summer (SS). Elements analysis was performed by atomic absorption spectrometry with flame (FAAS) and electrothermal (ETAAS) modes, using multielement standard solution. The obtained results show that, the trace and toxic elements (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and macronutrients (Al, Ca, K, Mg and Na) concentrations in lake water were above the recommended drinking water standards by WHO. Concentrations of Na detected in lake water in WS and SS, were in the range of 445.5-562.7 and 420.6-643.5 mgl(-1), respectively. While among toxic elements As concentration in both seasons, have been found in the range of 60.4-88.9 and 64.9-101.8 microgl(-1) respectively, these values are 6-10 times higher than the permissible limit of WHO. The mean concentrations of elements understudy in muscles of fish were found as 2.35, 1.39, 0.46, 2.3, 1517.9, 2.2, 2.4 and 188.9 mgkg(-1) for As, Cd, Cr, Cu, Fe, Ni, Pb and Zn, respectively. High accumulation of toxic elements in fish tissues is indicating that some of the metal contaminants are entering the food chain. Correlations among the variables were identified by multivariate analysis. The extraction of elements from sediments with EDTA, to predict the bioavailability of trace and toxic elements, has shown that among them As, Cd and Zn were the most bioavailable elements in lake sediment.     

Spectrophotometric determination of trifluralin in commercial formulations and agricultural samples using factorial design

A simple spectrophotometric method was developed for determination of trifluralin in commercial formulation and food samples. The method was based on the hydrolysis of trifluralin with sodium hydroxide to form 2,6-dinitro-4-trifluoromethylaniline. The resultant aniline group was diazotized with nitrate in acidic media and the diazotized product was coupled with β-naphthol to form red colored product having λ_max 550 nm. The reaction conditions were optimized for hydrolysis as well as for the diazotization reaction. The Beer’s law was obeyed over the range of 0.2–17 μg mL⁻¹ with molar absorptivity of 1.5 × 10⁴ L mol⁻¹ cm⁻¹. The relative standard deviation was found to be 3.6%. A two level factorial design of 2³ was used for optimization of all parameters. The influence of different factors and their interactions on the final azo dye formation were also studied from these factorial designs. The method has been applied successfully for the analysis of commercial formulations and agricultural samples. The recovery for the determination of trifluralin was found to be in the range 95–97%.