Chanbasha Basheer

Enhancement of Plant-Microbe Interactions Using a Rhizosphere Metabolomics-Driven Approach and Its Application in the Removal of Polychlorinated Biphenyls

Persistent organic pollutants, such as polychlorinated biphenyls (PCBs), are a global problem. We demonstrate enhanced depletion of PCBs using root-associated microbes, which can use plant secondary metabolites, such as phenylpropanoids. Using a “rhizosphere metabolomics” approach, we show that phenylpropanoids constitute 84% of the secondary metabolites exuded from Arabidopsis roots. Phenylpropanoid-utilizing microbes are more competitive and are able to grow at least 100-fold better than their auxotrophic mutants on roots of plants that are able to synthesize or overproduce phenylpropanoids, such as flavonoids. Better colonization of the phenylpropanoid-utilizing strain in a gnotobiotic system on the roots of flavonoid-producing plants leads to almost 90% removal of PCBs in a 28-d period. Our work complements previous approaches to engineer soil microbial populations based on opines produced by transgenic plants and used by microbes carrying opine metabolism genes. The current approach based on plant natural products can be applied to contaminated soils with pre-existing vegetation. This strategy is also likely to be applicable to improving the competitive abilities of biocontrol and biofertilization strains.

Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatography-mass spectrometry.

A simple and rapid liquid-phase microextraction (LPME) method using a hollow fiber membrane (HFM) in conjunction with gas chromatography-mass spectrometry (GC-MS) is presented for the quantitative determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 organochlorine pesticides (OCPs) in rainwater samples. The LPME conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of hollow fiber exposure time, stirring rate, sample pH, and composition. Enrichment factors of more than 100 could be achieved within 35 min of extraction with relative standard deviations (R.S.D.s) 1.3-13.6% for PAHs and 1.7-13.8% for OCPs, respectively, over a wide range of analyte concentrations. Detection limits ranged from 0.002 to 0.047 microg l(-1) for PAHs, and from 0.013 to 0.059 microg l(-1) for OCPs, respectively. The newly developed LPME-GC-MS method has been validated for the analysis of PAHs and OCPs in rainwater samples. Extraction recoveries from spiked synthetic rainwater samples varied from 73 to 115% for PAHs and from 75 to 113% for OCPs, respectively. Real rainwater samples were analyzed using the optimized method. The concentrations of PAHs and OCPs in real rainwater samples were between 0.005-0.162, and 0.063 microg l(-1), respectively.

Extraction of lead ions by electromembrane isolation

A new microextraction approach namely electromembrane isolation (EMI) coupled with capillary electrophoresis (CE) and ultraviolet (UV) detection for determining lead (Pb) ions was developed. The EMI technique involved the use of a polypropylene hollow fiber whose channel was filled with a sodium dihydrogen phosphate/sodium tetraborate buffer solution of pH 8.1, immersed in 10 mL of an aqueous sample solution. A voltage of 300 V was applied across the hollow fiber wall for 15 min to extract Pb ions. The extract was then complexed with ethylenediamminetetracetic acid (20 mM EDTA solution, at pH 3.4) for CE analysis. Satisfactory linear dynamic ranges (0.1-10 mg L(-1)), limits of detection (0.019 mg L(-1)) and good repeatability (ranging from 4.9 to 15.6%, n=3) were obtained. EMI exhibits good linearity with a correlation coefficient of 0.9935. The optimized EMI procedure was applied to determine the concentration of Pb(2+) in various matrices, such as amniotic fluid, blood serum, lipstick and urine samples.

Determination of carbamate pesticides using micro-solid-phase extraction combined with high-performance liquid chromatography

We describe a simple and sensitive porous polypropylene membrane-protected micro-solid-phase extraction (mu-SPE) approach for the sample preparation and determination of carbamate pesticides in soil samples by high-performance liquid chromatography. The mu-SPE device consisted of C(18) sorbent held within a porous polypropylene envelope. In order to achieve optimum performance, several extraction parameters were optimized. Under the most favorable conditions, the extraction efficiency of the mu-SPE was very high, with detection limits in the range of 0.01-0.40 ng g(-1). This is more than two orders of magnitude lower than the limits obtained by the United States Environmental Protection Agency Methods 8321A and 8318. A linear relationship was obtained for each analyte in the range of 2 and 200 ng g(-1). The relative standard deviation for the analysis of aged soil samples spiked at 5 ng g(-1) was < or = 11%. The reproducibility of separate mu-SPE device used for experiments was satisfactory (relative standard deviations ranged from 4 to 11%), indicating that the method is reliable for routine environmental analysis.

Simultaneous extraction of acidic and basic drugs at neutral sample pH: a novel electro-mediated microextraction approach.

The simultaneous extraction of acidic and basic analytes from a particular sample is a challenging task. In this work, electromembrane extraction (EME) of acidic non-steroidal anti-inflammatory drugs and basic β-blockers in a single step was carried out for the first time. It was shown that by designing an appropriate compartmentalized membrane envelope, the two classes of drugs could be electrokinetically extracted by a 300 V direct current electrical potential. This method required only a very short 10-min extraction time from a pH-neutral sample, with a small amount (50 μL) of organic solvent (1-octanol) as the acceptor phase. Analysis was carried out using gas chromatography-mass spectrometry after derivatization of the analytes. Extraction parameters such as extraction time, applied voltage, pH range, and concentration of salt added were optimized. The proposed EME technique provided good linearity with correlation coefficients from 0.982 to 0.997 over a concentration range of 1-200 μg L⁻¹. Detection limits of the drugs ranged between 0.0081 and 0.26 μg L⁻¹, while reproducibility ranged from 6 to 13% (n=6). Finally, the application of the new method to wastewater samples was demonstrated.

Organotin and Irgarol-1051 contamination in Singapore coastal waters

The seas surrounding Singapore are principally utilized by the shipping industry but are now also increasingly used for a variety of other purposes, including desalination for supplies of drinking water and intensive aquaculture of food fish. While stringent environmental pollution standards are in place for industrial effluents, there is currently no legislative control over pollution from anti-fouling paints in Singapore. In this study, the concentrations of toxic antifouling agents tributyltin (TBT), triphenyltin (TPhT) and Irgarol-1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) were determined from seawater obtained from 26 locations along and off the coast of Singapore in October and November 2000. These compounds were isolated by liquid-liquid extraction derivatized under controlled microwave heating and quantified by gas chromatography-mass spectrometry. TBT concentrations in seawater ranged between 0.43 and 3.20 microg 1(-1) with a mean value of 1.40 +/- 0.60 micro 1(-1). The mean values of DBT and MBT were 1.07 +/- 0.80 microg 11(-1) and 0.34 +/- 0.50 microg 1(-1) respectively, while TPhT concentrations of up to 0.40 microg 1(-1) were found. Monophenyltin and diphenyltin were not detected in all samples analysed. Irgarol-1051 was found to be present at concentrations of between 3.02 microg 1(-1) and 4.20 microg 1(-1) in seawater with a mean value of 2.00 +/- 1.20 microg 1(-1).

In situ derivatization hollow fibre liquid-phase microextraction for the determination of biogenic amines in food samples.

Hollow fibre liquid-phase microextraction with in situ derivatization using dansyl chloride has been successfully developed for the high-performance liquid chromatography-ultraviolet (HPLC-UV) determination of the biogenic amines (tryptamine, putrescine, cadaverine, histamine, tyramine, spermidine) in food samples. Parameters affecting the performance of the in situ derivatization process such as type of extraction solvent, temperature, extraction time, stirring speed and salt addition were studied and optimized. Under the optimized conditions (extraction solvent, dihexyl ether; acceptor phase, 0.1M HCl; extraction time, 30 min; extraction temperature, 26 degrees C; without addition of salt), enrichment factors varying from 47 to 456 were achieved. Good linearity of the analytes was obtained over a concentration range of 0.1-5 microg mL(-1) (with correlation coefficients of 0.9901-0.9974). The limits of detection and quantification based on a signal-to-noise ratio of 3-10, ranged from 0.0075 to 0.030 microg mL(-1) and 0.03 to 0.10 microg mL(-1), respectively. The relative standard deviations based on the peak areas for six replicate analysis of water spiked with 0.5 microg mL(-1) of each biogenic amine were lower than 7.5%. The method was successfully applied to shrimp sauce and tomato ketchup samples, offering an interesting alternative to liquid-liquid extraction and solid phase extraction for the analysis of biogenic amines in food samples.

Impact of nanoparticles on human and environment: review of toxicity factors, exposures, control strategies, and future prospects

Nanotechnology has revolutionized the world through introduction of a unique class of materials and consumer products in many arenas. It has led to production of innovative materials and devices. Despite of their unique advantages and applications in domestic and industrial sectors, use of materials with dimensions in nanometers has raised the issue of safety for workers, consumers, and human environment. Because of their small size and other unique characteristics, nanoparticles have ability to harm human and wildlife by interacting through various mechanisms. We have reviewed the characteristics of nanoparticles which form the basis of their toxicity. This paper also reviews possible routes of exposure of nanoparticles to human body. Dermal contact, inhalation, and ingestion have been discussed in detail. As very limited data is available for long-term human exposures, there is a pressing need to develop the methods which can determine short and long-term effects of nanoparticles on human and environment. We also discuss in brief the strategies which can help to control human exposures to toxic nanoparticles. We have outlined the current status of toxicological studies dealing with nanoparticles, accomplishments, weaknesses, and future challenges.

Liquid-phase and dispersive liquid-liquid microextraction techniques with derivatization: Recent applications in bioanalysis

Liquid phase microextraction (LPME), especially hollow fiber liquid-phase microextraction (HF-LPME), and dispersive liquid-liquid microextraction (DLLME) offer high enrichments of target analytes in a single step. The analytical usefulness of these techniques is significantly enhanced by coupling them with suitable derivatization methods. Due to their simplicity, diverse bioanalytical applications have recently been reported. This review focuses on the recent developments of the combined LPME (mainly HF-LPME and single drop microextraction (SDME)) and DLLME techniques with derivatization for the analysis of biological samples. A broad range of sample matrices such as urine, blood, plasma and human hair samples with various derivatization methods for polar or ionizable organic compounds will be considered. These techniques can also be extended to the determination of trace metal ions, such as the heavy metal ions (Hg, Pb, and Co) and Se. Future trends of the techniques will also be discussed.

Ionic liquid supported three-phase liquid-liquid-liquid microextraction as a sample preparation technique for aliphatic and aromatic hydrocarbons prior to gas chromatography-mass spectrometry.

For the first time hollow fiber-protected ionic liquid supported three-phase (liquid-liquid-liquid) microextraction (HFM-LLLME) was developed for the gas chromatography-mass spectrometric (GC-MS) analysis of aromatic and aliphatic hydrocarbons. The hydrocarbons were extracted from 10 ml of aqueous samples though small volumes of ionic liquid and organic solvent in the hollow fiber membrane HFM) wall and channel, respectively. The ionic liquid was immiscible with both the aqueous sample and the organic solvent (toluene). After extraction, the enriched solvent was directly injected into a GC-MS system for analysis without any further pretreatment. Ionic liquid supported HFM-LLLME shows better extraction performance than two-phase HFM-liquid-phase microextraction, in which only organic solvent is involved, and solid-phase microextraction. The ionic liquid and organic solvent combination found most suitable for HFM-LLLME was 1-butyl-3-methylimidazolium hexafluorophosphate, and toluene, respectively. This new technique provided up to 210-fold enrichment of aliphatic and aromatic hydrocarbons in 40 min with good reproducibility (<11%) and limits of detection (1-7 ng l(-1)).