Simple and efficient ion imprinted polymer for recovery of uranium from environmental samples.

Ion imprinted polymer material (IIP) was prepared by forming ternary complexes of uranyl imprint ion with 1-(prop-2-en-1-yl)-4-(pyridin-2-ylmethyl)piperazine and methacrylic acid followed by thermal copolymerization with ethylene glycol dimethacrylate as the cross-linking monomer in the presence of 1,1'-azobis(cyclohexanecarbonitrile) initiator and 2-methoxy ethanol porogenic solvent. HCl solution (5 mol/L) was used to leach out the uranyl template ion from the IIP particles. Similarly, the control polymer (CP) material was also prepared exactly under the same conditions as the IIP but without the uranyl ion template. Various parameters such as solution pH, initial concentration, aqueous phase volume, sorbent dosage, contact time and leaching solution volumes were investigated. SEM, IR and BET-surface area and pore size analysis were used for the characterization of IIP and CP materials. The extraction efficiency of the IIP and CP was compared using a batch and SPE mode of extraction. The optimal pH for quantitative removal is 4.0-8.0, sorbent amount is 20 mg, contact time is 20 min and the retention capacity is 120 mg of uranyl ion per g of IIP. The IIP prepared demonstrated superior selectivity towards coexisting cations and therefore it can be used for selective removal of uranium from complex matrices.

Natural radioactivity and trace metals in crude oils: implication for health.

Crude oil samples were collected from six different fields in the central Niger Delta in order to determine their natural radioactivity and trace element contents, with the aim of assessing the radiological health implications and environmental health hazard of the metals, and also to provide natural radioactivity baseline data that could be used for more comprehensive future study in this respect. The activity concentrations of the radionuclides were measured using a well, accurately calibrated and shielded vertical cryostat, Canberra coaxial high-purity germanium (HPGe) detector system, and the derived doses were evaluated. The metal concentrations were determined by the graphite furnace atomic absorption spectroscopic (GFAAS) method. The radionuclides identified with reliable regularity belong to the decay series of naturally occurring radionuclides headed by (238)U and (232)Th along with the non-decay series radionuclide, (40)K. The averaged activity concentrations obtained were 10.52 +/- 0.03 Bq kg(-1), 0.80 +/- 0.37 Bq kg(-1) and 0.17 +/- 0.09 Bq kg(-1) for (40)K, (238)U and (232)Th, respectively. The equivalent doses were very low, ranging from 0.0028 to 0.012 mSv year(-1) with a mean value of 0.0070 mSv year(-1). The results obtained were low, and hence, the radioactivity content from the crude oils in the Niger delta oil province of Nigeria do not constitute any health hazard to occupationally exposed workers, the public and the end user. The concentrations of the elements (As, Cd, Co, Fe, Mn, Ni, Se and V) determined ranged from 0.73 to 202.90 ppb with an average of 74.35 ppb for the oil samples analysed. The pattern of occurrence of each element agreed with the earlier studies from other parts of the Niger Delta. It was obvious from this study and previous ones that the Niger Delta oils have low metal contents. However, despite the low concentrations, they could still pose an intrinsic health hazard considering their cumulative effects in the environment. Also, various studies on the impact of oil spillage and activities of oil exploration and production on organisms in the immediate environment suggest this.

Enzymatic specificity and hydrolysis pattern of the catalytic domain of the xylanase Xynl from Rhodothermus marinus.

The catalytic domain of a xylanase from Rhodothermus marinus was produced in Escherichia coli. The catalytic domain belongs to glycosyl hydrolase family 10. The produced protein has a 22-amino acid leader peptide followed by a 411-amino acid truncated xylanase. The molecular mass was 48 kDa and the recombinant xylanase had a pI of 4.9. The pH and temperature optima for activity were determined to be 7.5 and 80 degrees C, respectively. At that temperature the enzyme had a half-life of 1 h 40 min. An addition of 1 mM calcium stabilized the activity of the enzyme at 80 degrees C. The xylanase had its highest specific activity on oat spelt xylan but was active also on other xylans and to a limited extent on some other polysaccharides (soluble glucans). No exo- or endo-cellulase activity was observed. Hydrolysis of xylo-oligomers and oat spelt xylan was studied and the predominant products of hydrolysis were xylobiose and xylotriose. The enzyme was inactive on xylobiose, xylotriose and on the soluble fraction from oat spelt xylan. The R. marinus xylanase is shown to have a strong preference for internal linkages and is therefore classified as an endo-xylanase.

Hydrolytic properties of a beta-mannosidase purified from Aspergillus niger.

A beta-mannosidase was purified to homogeneity from the culture filtrate of Aspergillus niger. A specific activity of 500 nkat mg-1 and a 53-fold purification was achieved using ammonium sulfate precipitation, anion-exchange chromatography, and gel filtration. The isolated enzyme has an isoelectric point of 5.0 and appears to be a dimer composed of two 135-kDa subunits. It is a glycoprotein and contains 17% N-linked carbohydrate by weight. Maximal activity was observed at pH 2.4 5.0 and at 70 degrees C. The beta-mannosidase hydrolyzed beta-1,4-linked manno-oligosaccharides of degree of polymerization (DP) 2-6 and also released mannose from polymeric ivory nut mannan and galactomannan. The Km and Vmax values for p-nitrophenyl-beta-D-mannopyranoside were 0.30 mM and 500 nkat mg-1, respectively. Hydrolysis of D-galactose substituted manno-oligosaccharides showed that the beta-mannosidase was able to cleave up to, but not beyond, a side group. An internal peptide sequence of 15 amino acids was highly similar to that of an Aspergillus aculeatus beta-mannosidase belonging to family 2 of glycosyl hydrolases.

Optimal membrane choice for microdialysis sampling of oligosaccharides.

An analytical methodology based on microdialysis sampling, high-performance anion-exchange chromatography and integrated pulsed electrochemical detection for the monitoring of oligosaccharides in bioprocesses is presented. Amylopectin and model maltooligosaccharide standards; glucose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose and maltoheptaose were used to demonstrate its versatility in view to sampling in enzymatic bioprocesses. The performance and characteristics of membranes with the same cut-off ranging between 3 and 100 kDa, were evaluated with respect to their extraction fraction (EF), permeability factors, temperature stability and protein (enzyme) interaction. All investigated membranes showed some non-specific interaction with enzymes. The EF and non-specific membrane-enzyme interactions were higher for the polysulfone membranes compared with the polyamide and polyethersulfone membranes. For all saccharides, the EF was independent of the concentration even for a 250-fold change in concentration. The EF and morphology of the membranes in their dehydrated state, as observed using scanning electron microscopy did not show any significant difference between membranes exposed to a 90 degrees C temperature for 3 and 24 h indicating their applicability to the study of high temperature bioprocesses.

Electrospun nanofiber based colorimetric probe for rapid detection of Fe2+ in water.

An imidazole derivative, 2-(2'-pyridyl)imidazole (PIMH), was developed as a colorimetric probe for the qualitative analysis of Fe(2+) in aqueous solution. PIMH was then used to post-functionalize poly(vinylbenzyl chloride) (PVBC) nanofibers after electrospinning so as to afford a solid state colorimetric probe. Upon treatment with Fe(2+) the probe displayed a distinctive color change both in liquid and solid platforms. The linear dynamic range for the colorimetric determination of Fe(2+) was 0.0988-3.5 µg mL(-1). The ligand showed a high chromogenic selectivity for Fe(2+) over other cations with a detection limit of 0.102 µg mL(-1) in solution (lower than the WHO drinking water guideline limit of 2 mg L(-1)), and 2 µg mL(-1) in the solid state. The concentration of Fe(2+) in a certified reference material (Iron, Ferrous, 1072) was found to be 2.39±0.01 mg L(-1), which was comparable with the certified value of 2.44±0.12 mg L(-1). Application of the probe to real samples spiked with Fe(2+) achieved recoveries of over 97% confirming accuracy of the method and its potential for on-site monitoring.

Heavy metals pollution in a sewage treatment oxidation pond and the receiving stream of the Obafemi Awolowo University, Ile Ife, Nigeria.

This work centered on a 1-year evaluation campaign of point source pollution from a sewage treatment oxidation pond and its receiving stream. Water samples were collected from the sewage treatment oxidation pond and the receiving stream during July 2002 and June 2003. Concentrations of heavy metals were determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) after a triple acid digestion of samples using open beaker method. Generally, the results showed high levels of toxic metals such as Cd, Pb, As, Al, Cr, Mn, Co, and Fe in the influent and effluent samples as well as in the receiving stream. The annual mean concentration of metals in the sewage samples ranged from 11.90 to 16.05, 64.96 to 88.27, 38.91 to 76.35, 17.46 to 24.45 mug/L for Cd, As, Pb, Co, and 4.31 to 8.77, 1.71 to 2.45, 0.46 to 0.74 and 13.82 to 20.47 mg/l for Al, Cr, Mn and Fe, respectively; while in the receiving stream, the concentrations were between 6.89 to 10.45, 35.50 to 59.26, 22.85 to 35.94, 11.33 to 18.83 mug/l for Cd, As, Pb, Co, and 1.99 to 3.49, 1.35 to 2.08, 0.21 to 0.48, and 8.93 to 14.15 mg/l for Al, Cr, Mn and Fe, respectively. The discharge of the effluent from the sewage pond into the receiving stream has therefore led to increase in the concentrations of some heavy metals downstream, thus impacting the receiving stream negatively and could pose a serious health hazard to aquatic ecosystems and humans particularly for rural dwellers and peasant farmers downstream that utilize the water from the receiving stream for various domestic and agricultural purposes untreated.

Survey of levels of phthalate ester plasticizers in a sewage lagoon effluent and a receiving stream.

In this study, samples from a sewage treatment lagoon and those from a receiving stream were analyzed for their phthalate esters content. Knowledge of the distribution of ubiquitous phthalate esters in the sewage lagoon and the receiving stream was necessary because of the reports of their subtle toxicity to aquatic biota and humans. Liquid-liquid extraction, Clean-up experiment and High Performance Liquid Chromatography (HPLC) were the methods employed for the quantitative determination of the Phthalates. A study of uncontaminated water was done to establish blank levels. The sewage lagoon and the receiving stream were grossly polluted as several phthalate ester plasticizers: DMP, DEP, DPhP, DBP, DEHP, DOP and DINP were found present at monthly mean levels of between 24.02 mg/L and 139.25 mg/L in the sewage treatment lagoon and 10.41 mg/L and 80.53 mg/L in the receiving stream. The results showed higher levels of phthalate esters in the sewage lagoon compared to the receiving stream. The sewage lagoon was identified as a pollution point source into the receiving stream. Levels of phthalates obtained from the receiving stream are much higher than the water criteria of 3 microg/L phthalates recommended by the United States Environmental Protection Agency (USEPA) for the protection of fish and other aquatic life in water and the Suggested No-Adverse Effect Levels (SNAEL) of 7.5-38.5 microg/L for drinking water. This should give cause for great environmental concern. Peoples' health downstream is at stake and so is the 'health' of the ecosystem.

Evaluation of yeast strains as possible agents for trace enrichment of metal ions in aquatic environments.

Sorption properties of six yeast strains were evaluated for trace enrichment of metal ions; Cd(2+), Cr(3+), Cr(6+), Cu(2+), Pb(2+), and Zn(2+) from aqueous environments. Metal concentration was determined by flame atomic absorption spectrometry (FAAS). The results showed that trace enrichment of the metals under study with yeast, was dependent on the pH and available metal ions. Enrichment time of 30min gave an optimum metal uptake. The presence of Na(+), K(+), and Ca(2+) suppressed the uptake of Pb by less than 5%, but suppressed the uptake of Zn by between 15 and 25%. Mg(2+), Cu(+), Cu(2+), Cr(3+) Cr(6+), Cd(2+), and Zn(2+) suppressed the uptake of Pb by between 25 and 35%, and that of Zn by between 15 and 25%. For both Pb and Zn, Cd had the highest suppression of 35 and 30%, respectively for baker's yeast (Saccharomyces cerevisiae). Baker's yeast achieved enrichment factors (EF) of 23, 4, 100, and 1 for dam water, stream water, treated wastewater, and industrial effluent samples for Cu, Pb, Zn, and Cr, respectively. The recoveries of optimised Cd and Cr samples spiked with 2mugml(-1) of the metal could reach up to 90%, but never exceeded 66% for 10mugml(-1) samples. For Cu and Pb, the recoveries generally increased independent of concentration, however they were not as high as those for Zn, which exceeded 90% for all the samples spiked with 10mugml(-1) of the metal. S. cerevisiae PR 61/3 had the highest EF for Cr as compared to the other yeast strains. S. cerevisiae PRI 60/78 was the only yeast strain which was able to enrich Cd in all the samples. Baker's yeast had the highest EFs for Cu and Zn as compared to the other yeast strains without pH adjustment of the water samples. Candida tropicalis attained the highest EFs for Pb as compared to the other yeast strains. The results indicate that all the yeast strains used had a high affinity for Zn based on the EF values achieved. The results from these studies demonstrate that yeast is a viable trace metal enrichment agent that can be used freely suspended in solution to enrich metal ions at relatively low concentrations. This has ramifications on the traditional methods of sampling, sample collection, and transportation from remote sampling sites.

Trace enrichment of metal ions in aquatic environments by Saccharomyces cerevisiae.

Sorption properties of baker's yeast cells, characterised as Saccharomyces cerevisiae were evaluated for trace enrichment of metal ions: Cd(2+), Cr(3+), Cr(6+), Cu(2+), Pb(2+) and Zn(2+) from aqueous environments. Metal concentration was determined by flame atomic absorption spectrometry (FAAS). Parameters affecting metal uptake such as solution pH, incubation time, amount of yeast biomass and effect of glucose concentration (energy source) were optimised. Further studies were carried out to evaluate the effects on metal uptake after treating yeast with glucose as well as with an organic solvent. The results showed that trace enrichment of the metals under study with yeast, depends upon the amount of yeast biomass, pH and incubation time. Treatment of yeast cells with 10-20mM glucose concentration enhanced metal uptake with exception to Cr(6+), whose metal enrichment capacity decreased at glucose concentration of 60mM. Of the investigated organic solvents THF and DMSO showed the highest and lowest capacity, respectively, to enhance metal uptake by yeast cells. Trace enrichment of metal ions from stream water, dam water, treated wastewater from a sewage plant and wastewater from an electroplating plant achieved enrichment factors (EF) varying from 1 to 98, without pre-treatment of the sample. pH adjustment further enhanced the EF for all samples. The results from these studies demonstrate that yeast is a viable trace metal enrichment media that can be used freely suspended in solution to achieve very high EF in aquatic environments.

Monitoring of enzymatic hydrolysis of starch by microdialysis sampling coupled on-line to anion exchange chromatography and integrated pulsed electrochemical detection using post-column switching.

A quantitative evaluation of the hydrolysis of wheat starch using Termamyl, a thermostable alpha-amylase (endo-1,4-alpha-d-glucan, glucanohydrolase; EC 3.2.1.78), is reported. Data from the monitoring of the hydrolysis of wheat starch indicated that, after 1 h, glucose and maltooligosaccharides up to DP 7 were the main hydrolysis products and thus enabled optimization of a liquefication step during the production of L-lactic acid. The monitoring system used, both in the on- and off-line mode, was based on continuous flow microdialysis sampling (CFMS) coupled to anion exchange chromatography and integrated pulsed electrochemical detection (IPED). A microdialysis probe equipped with a 5-mm polysulfone (SPS 4005) membrane, with a molecular-weight cut-off of 5 kDa, was used to sample the hydrolysis products of native wheat starch at 90 degrees C. Characteristic fingerprint separations were achieved by anion exchange chromatography after enzymatic hydrolysis. Post-column switching improved the detection and, consequently, also quantification of the hydrolysates as fouling of the electrode could be reduced. Maltooligosaccharide standards were used for quantification and to verify the elution of the hydrolysates by spiking the off-line samples. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 56: 546-554, 1997.