Fabrication and applications of ultrafine powder from cashmere guard hair

Cashmere guard hair, an industrial animal protein fibre waste material has been very first time converted into ultra-fine powder particles. The work also demonstrates potential of the newly developed particles in high value technical applications such as toxic heavy metal ion separation and surface functionalization of textile fabrics.

Comparative analyses of cadmium and zinc uptake correlated with changes in natural resistance-associated macrophage protein (NRAMP) expression in Solanum nigrum L. and Brassica rapa

Environmental context Soils contaminated with metals can pose both environmental and human health risks. This study showed that a common crop vegetable grown in the presence of cadmium and zinc readily accumulated these metals, and thus could be a source of toxicity when eaten. The work highlights potential health risks from consuming crops grown on contaminated soils. Abstract Ingestion of plants grown in heavy metal contaminated soils can cause toxicity because of metal accumulation. We compared Cd and Zn levels in Brassica rapa, a widely grown crop vegetable, with that of the hyperaccumulator Solanum nigrum L. Solanum nigrum contained 4 times more Zn and 12 times more Cd than B. rapa, relative to dry mass. In S. nigrum Cd and Zn preferentially accumulated in the roots whereas in B. rapa Cd and Zn were concentrated more in the shoots than in the roots. The different distribution of Cd and Zn in B. rapa and S. nigrum suggests the presence of distinct metal uptake mechanisms. We correlated plant metal content with the expression of a conserved putative natural resistance-associated macrophage protein (NRAMP) metal transporter in both plants. Treatment of both plants with either Cd or Zn increased expression of the NRAMP, with expression levels being higher in the roots than in the shoots. These findings provide insights into the molecular mechanisms of heavy metal processing by S. nigrum L. and the crop vegetable B. rapa that could assist in application of these plants for phytoremediation. These investigations also highlight potential health risks associated with the consumption of crops grown on contaminated soils.

Capsular polypyrrole hollow nanofibers: an efficient recyclable adsorbent for hexavalent chromium removal

Capsular polypyrrole hollow nanofibers (PPy-HNFs) were fabricated via in situ polymerization of pyrrole on an organic-inorganic template, followed by acid etching. Their application in removing hexavalent chromium (Cr(vi)) from aqueous solution was then investigated. The morphologies of the capsular PPy-HNFs were studied by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which showed that the PPy-HNFs had a capsular structure in the walls of hollow nanofibers. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) data confirmed the adsorption of Cr on capsular PPy-HNFs. The adsorption capacity increased with reduced pH of the initial solution and the adsorption process can be described using the pseudo-second-order model. These capsular PPy-HNFs showed a high Cr(vi) adsorption capacity up to 839.3 mg g-1. This adsorption capacity was largely retained even after five adsorption/desorption cycles. Electrostatic attraction between Cr and PPy-HNFs was studied using a proposed adsorption mechanism. The capsular PPy-HNFs formed a flexible membrane, which allowed easy handling during application. This study has demonstrated the possibilities of using this capsular PPy-HNF membrane for heavy metal removal from aqueous solution.

On-site determination of Pb2+ and Cd2+ in seawater by double stripping voltammetry with bismuth-modified working electrodes

To meet the urgent requirement of determining trace Pb2+ and Cd2+ in seawater on site, herein we developed a simple but novel electrochemical method, named as double stripping voltammetry, using only a portable heavy metal analyzer. The proposed method consisted of three steps: First, the targeted heavy metal ions in bulk solution were concentrated onto an ionic liquid-graphite-based paste working electrode (ILGPE), which exhibits a dramatic ability of accumulation, by electrodeposition in the presence of Bi3+. Second, the three-electrode arrangement, including the ILGPE loaded with the reduced products, was transferred into 1.0mL acetate buffer solution, followed by a stripping procedure. Third, the measurement was performed with the other stripping voltammetry procedure by using a glassy carbon electrode as working electrode. Under optimum conditions, the linear range values for Pb2+ and Cd2+ in seawater were 0.2-3.2 μg/L and 0.1-3.2 μg/L, respectively. The concentrations of Pb2+ and Cd2+ in five real samples collected from coastal sites of Qingdao City were determined on site, and the results were in good agreement with that obtained with the atomic absorption spectroscopy method. In addition, the analytical performance of working electrode modified with Bi film by in situ mode was investigated in comparison with that by ex situ mode. The results showed that the in situ mode was much better than the ex situ one.

Observations of metal concentrations in tilapia (Oreochromis mossambicus)in reservoirs of South Sri Lanka

Samples of the muscle and liver of tilapia (Oreochromis mossambicus) obtained from the five reservoirs in four catchments in southern Sri Lanka in 1998 were analyzed for 16 elements: As, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn by inductively coupled plasma emission spectrophotometry, and Hg by atomic absorption spectrophotometry. The concentrations of Cr, Ni, and Pb were below the detection limits of the instrumental techniques employed in all samples. The elements As, Ca, Co, Cu, Fe, Hg, K, Mg, Mn, Na, Sr, and Zn were detected in the muscle and liver tissue, with Cd detected in some liver samples. There were no statistically significant differences between the individual concentrations of any of the metals and the site from which the tilapia were collected (P>0.05). Furthermore, no statistically significant correlations were found between total length of fish and metal concentration. No elements were found at concentrations of toxicological concern. However, a principal component analysis suggests that the populations of tilapia in the reservoirs may be exposed to different regimes of metals, possibly associated with different catchment land-use patterns.

Aqueous/micellar peroxyoxalate chemiluminescent detection for ion chromatography

This thesis covers the development of the traditionally fluorescent bis(8-quinolinol-5-sulfonic acid) magnesium (II) fluorophore as a chemiluminescent emitter. A brief description of luminescence spectroscopy and its application to analytical chemistry lays the foundation to the discussion of the results obtained herein. This includes the synthesis and identification of two so called ‘water soluble’ aryl oxamides 2,2’-oxalyl-bis(trifluoromethanesulfonyl) imino] ethylene-bis(N- methylpyridinium) trifluoromethane sulfonate (PETQ) and 2,2’-oxalyl-bis(trifluoromethanesulfonyl) imino]ethylene-bis(N-pyridinium) chloride (PETH), previously developed for the US navy as a possible emergency light source, yet the synthetic methodology were incomplete. The inconsistencies of the synthetic methods for PETQ and PETH were overcome with yields satisfactory for their preliminary analytical evaluation. The evaluation of these aryl oxamides, including 4,4’-oxalyI- bis[(trifluoromethanesulfonyl) imino]ethylene-bis(l-methyM-benzylpiperidinium) trifluoromethanesulfonate (BPTQ), 4,4’-oxalyl-bis [(trifluoromethylsulfonyl)imino] ethylene-bis(N-methylmorpholinium)trifluoromethanesulfonate (METQ) and the oxalate bis(2,4,6-trichlorophenyl) oxalate (TCPO) were performed with the peroxyoxalate chemiluminescent reaction using bis(8-quinolinol-5-sulfonic acid) magnesium (II) as the fluorophore. A univariate optimisation of this system resulted in 0,0082 mol 1-1 the detection limit of magnesium in the absence of cationic surfactants and 0.0041 mol 1-1 in their presence for the majority of these compounds. The oxamides were found to be insoluble in water with long ulrasonication periods required to dissolve the compound, with solvents such as acetonitrile preferred. The determination of other chemiluminescent metal-8HQS chelates to replace magnesium -8HQS in the peroxyoxalate were limited to Al (III), Cd (II), Ca (II), In (II) and Zn (II), unfortunately these metals all possessed poorer detection limits than those obtained using magnesium The base reaction conditions used for the flow injection system with chemiluminescent detection were transferred to an ion chromatographic configuration for the separation of magnesium from other cations on an exchange column. After a univariate and simplex optimisation of these conditions, the detection limit of magnesium was found to be 0.0411 mol 1-1 which was less than the limits that could be achieved with fluorescent detection, The further development of this reaction to incorporate the displacement of magnesium from Mg-EDTA by other metals that possessed a higher conditional stability constant than magnesium also proved to be problematic with interferences from not only EDTA but from the eluant (lactic acid) from the cation column. Using this system the detection limits of the displacing metals were found to be in the order of 10 mg 1-1 which was substantially less that what was observed when exactly the same configuration was used with fluorescent detection. The final component of the thesis entails the discussion of the background emission that results from the reaction of oxamides/oxalates with hydrogen peroxide. A detailed investigation into the reaction of TCPO and hydrogen peroxide in the presence of various additives, such as imidazole , heavy atoms and triethylamine illustrated the existence of a further intermediate in fee mechanism for this reaction. The species responsible for this emission was attributed to the degradation product 2,4,6-trichlorophenyi of TCPO, which was supported by the non-existent background present with the oxamides that do not contain this degradation product.

Improved membranes for the extraction of heavy metals

This work presents a series of experimental tests on new practical approaches in membrane design to improve extraction capacity and rate. We chose an extraction system involving Aliquat 336 as the extractant and Cd(II) as the metal ion to be extracted to demonstrate these new approaches. The core element in the new membrane assembly was the extractant loaded sintered glass filter. This membrane assembly provided a large interface area between the extractant and the aqueous solution containing metal ions. By recycling the aqueous solution through the membrane assembly, the extraction rate was significantly improved. The membrane assembly also offered good extraction capacity.

Fast scene change detection based histogram

This work presents a new approach to detecting the scene change in the successive capture of photographs of a place within equal time interval. This method is based on a gray level histogram of every image. In this method the histogram of an image is processed to modify it for matching with the processed histogram of a reference image. The coefficient of correlation is taken as the measure of matching. As the method does not do any heavy signal processing, and the images are taken successively with a multi-shot digital still camera, it can be applied for real-time processing of such pictures for detection of a scene change. A multi-camera in multi-position approach is also shown to evaluate the change in scene simultaneously from different angles. Both multi-camera and single-camera approaches are compared in detecting a scene change.

Observations on the effects of caged carp culture on water and sediment metal concentrations in Lake Kasumingaura, Japan

The concentrations of 24 elements in the sediment and associated water column were monitored at two sites, one an area of intensive cage culture of carp, the other a wild site far from known cage culture areas, in Lake Kasumigaura, Japan, between September 1994 and September 1995. The concentrations of most elements in Lake Kasumigaura are mostly sub-parts per billion, except those for Ca, Fe, K, Mg, Na, P, and Si. The concentrations of Cd, Co, Cu, Mn, Ni, Pb, V, and Fe in Lake Kasumigaura are higher than the values in Lake Mashu, Lake Shikotsu, and Lake Biwa, and comparable to the levels in open ocean. Statistically significant differences in metal concentrations were observed between the culture and wild sites, with metal concentrations consistently higher at the culture site. Although cage culture of carp in the Lake Kasumigaura system may be causing localized increase in metal concentrations in the sediments, we must treat the results with caution, since the concentrations of metals observed in the sediments in 1995 were lower than those observed in 1979 for all metals at both sampling sites. In conclusion, further study of the concentrations of metals in the lake as a whole must be undertaken before the differences between the culture and wild sites can be proved, or disproved, to be the result of carp culture.

Trace metal concentrations in edible tissue of snapper, flathead, lobster, and abalone from coastal waters of Victoria, Australia

The concentrations of heavy metals in the edible tissue of commonly fished species of the Victorian coast of Australia are reported. The metals studied were As, Cd, Cu, Hg, Pb, Se, and Zn and the fish species examined were snapper (Pagruss auratus), flathead (Platycephalus bassenssis and Neoplatycephalus richardsoni), lobster (Jasus edwardsii), and abalone (Haliotis rubra). None of the fish species studied had average concentrations exceeding the maximum levels specified for As, Cd, Hg, and Pb by the Food Standards Australia and New Zealand Food Standards code. Additionally, the concentrations of Cu, Se, and Zn were close to or below the median values generally expected in these species. Essential trace elements Se and Zn were found to be well regulated by all fish species. Although also essential, Cu was not so well regulated, especially in abalone. Nonessential metals As, Cd, and Hg are not regulated in the studied fish and their concentrations in the fish tissue are dependent on size and fishing zone. Metal concentrations were not largely affected by sex. Surprisingly, the concentrations of metals in fish in Port Phillip Bay, a zone, which includes the major cities of Melbourne and Geelong and is known to have high concentrations of metals in the water and sediment, were not consistently higher than those in other less-populated fishing zones.

Sub-ppt detection limits for copper ions with Gly-Gly-His modified electrodes

An electrochemical metal ion sensor has been developed with a detection limit of less than 0.2 ppt by the covalent attachment of the tripeptide Gly-Gly-His as a recognition element to a 3-mercaptopropionic acid modified gold electrode.