Intelligent potentiostat for identification of heavy metals in situ

This article presents a low-cost portable electrochemical instrument capable of on-site identification of heavy metals. The instrument acquires metal-specific voltage and current signals by the application of differential pulse anodic stripping voltammetry. This technique enhances the analytical current and rejects the background current, resulting in a higher signal-to-noise ratio for a better detection limit. The identification of heavy metals is based on an intelligent machine-based method using a multilayer perceptron neural network consisting of three layers of neurons. The neural network is implemented using a 16 bit microcontroller. The system is developed for use in the field in order to avoid expensive and time-consuming procedures and can be used in a variety of situations to help environmental assessment and control. 

Permutation entropy based real-time chatter detection using audio signal in turning process

Machine tool chatter is an unfavorable phenomenon during metal cutting, which results in heavy vibration of cutting tool. With increase in depth of cut, the cutting regime changes from chatter-free cutting to one with chatter. In this paper, we propose the use of permutation entropy (PE), a conceptually simple and computationally fast measurement to detect the onset of chatter from the time series using sound signal recorded with a unidirectional microphone. PE can efficiently distinguish the regular and complex nature of any signal and extract information about the dynamics of the process by indicating sudden change in its value. Under situations where the data sets are huge and there is no time for preprocessing and fine-tuning, PE can effectively detect dynamical changes of the system. This makes PE an ideal choice for online detection of chatter, which is not possible with other conventional nonlinear methods. In the present study, the variation of PE under two cutting conditions is analyzed. Abrupt variation in the value of PE with increase in depth of cut indicates the onset of chatter vibrations. The results are verified using frequency spectra of the signals and the nonlinear measure, normalized coarse-grained information rate (NCIR).

Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases

One of the main challenges in the development of metal-oxide gas sensors is enhancement of selectivity to a particular gas. Currently, two general approaches exist for enhancing the selective properties of sensors. The first one is aimed at preparing a material that is specifically sensitive to one compound and has low or zero cross-sensitivity to other compounds that may be present in the working atmosphere. To do this, the optimal temperature, doping elements, and their concentrations are investigated. Nonetheless, it is usually very difficult to achieve an absolutely selective metal oxide gas sensor in practice. Another approach is based on the preparation of materials for discrimination between several analyte in a mixture. It is impossible to do this by using one sensor signal. Therefore, it is usually done either by modulation of sensor temperature or by using sensor arrays. The present work focus on the characterization of n-type semiconducting metal oxides like Tungsten oxide (WO3), Zinc Oxide (ZnO) and Indium oxide (In2O3) for the gas sensing purpose. For the purpose of gas sensing thick as well as thin films were fabricated. Two different gases, NO2 and H2S gases were selected in order to study the gas sensing behaviour of these metal oxides. To study the problem associated with selectivity the metal oxides were doped with metals and the gas sensing characteristics were investigated. The present thesis is entitled “Development of semiconductor metal oxide gas sensors for the detection of NO2 and H2S gases” and consists of six chapters.

Fully electrochemical hyphenated flow system for preconcentration, cleanup, stripping, capillary electrophoresis with stacking and contactless conductivity detection of trace heavy metals

Successful coupling of electrochemical preconcentration (EPC) to capillary electrophoresis (CE) with contactless conductivity detection (C(4)D) is reported for the first time. The EPC-CE interface comprises a dual glassy carbon electrode (GCE) block, a spacer and an upper block with flow inlet and outlet, pseudo-reference electrode and a fitting for the CE silica column, consisting of an orifice perpendicular to the surface of a glassy carbon electrode with a bushing inside to ensure a tight press fit. The end of the capillary in contact with the GCE is slant polished, thus defining a reproducible distance from the electrode surface to the column bore. First results with EPC-CE-C(4)D are very promising, as revealed by enrichment factors of two orders of magnitude for Tl, Cu, Pb and Cd ion peak area signals. Detection limits for 10 min deposition time fall around 20 nmol L(-1) with linear calibration curves over a wide range. Besides preconcentration, easy matrix exchange between accumulation and stripping/injection favors procedures like sample cleanup and optimization of pH, ionic strength and complexing power. This was demonstrated for highly saline samples by using a low conductivity buffer for stripping/injection to improve separation and promote field-enhanced sample stacking during electromigration along the capillary. (C) 2010 Elsevier B.V. All rights reserved.

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.

Heavy metals in Oxisols amended with biosolids and cropped with maize in a long-term experiment

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Selective UV-filter detection with sensors based on stainless steel electrodes modified with polyaniline doped with metal tetrasulfonated phthalocyanine films

This work describes the construction and application of two amperometric sensors for sensitive UV-filter determination. The sensors were prepared using stainless steel electrodes in which polyaniline (PANI) was electrochemically polymerized in the presence of nickel (NiPcTS) or iron (FePcTS) tetrasulfonated phthalocyanines. The sensor surface characterizations were carried out using atomic force microscopy (AFM). The PANI/NiPcTS sensor was selective for the chemical UV-filter p-aminobenzoic acid (PABA) and the PANI/FePcTS sensor was selective for octyldimethyl-PABA (ODP), both in a mixture of tetrahydrofuran (THF) and 0.1 mol L(-1) H(2)SO(4) at a volume ratio of 30 : 70, and with an applied potential of 0.0 mV vs. Ag vertical bar AgCl. A detailed investigation of the selectivity was carried out for both sensors, in order to determine their responses for ten different UV filters. Finally, each sensor was successfully applied to PABA or ODP quantification in sunscreen formulations and water from swimming pools.

Assessment of anaerobic sewage sludge quality for agricultural application after metal bioleaching

The effects of metal bioleaching on nutrient solubilization, especially nitrogen and phosphorous, from anaerobically-digested sewage sludge were investigated in this work. The assessment of the sanitary quality of the anaerobic sludge after bioleaching was also carried out by enumerating indicator (total coliforms, fecal coliforms, and fecal streptococci) and total heterotrophic bacteria. The experiments of bioleaching were performed using indigenous sulphur-oxidizing bacteria (Thiobacillus spp.) as inoculum and samples of anaerobically-digested sludge. Nitrogen and phosphorous solubilization from sewage sludge was assessed by measuring, respectively, the concentration of Total Kjeldahl Nitrogen, ammonia, nitrate/nitrite, and soluble and total phosphorous before and after the bioleaching assays. At the end of the experiment, after 4 days of incubation (final pH of 1.4), the following metal solubilization yields were obtained: zinc, 91%; nickel, 87%; copper, 79%; lead, 52%; and chromium, 42%. As a result of sludge acidification, the viable counts of selected indicator bacteria were decreased to below the detection limit (4 × 103 cfu 100 ml-1), followed by an increase in the mineral fraction of nitrogen (from 6 to 10%) and in the soluble fraction of phosphorous (from 15 to 30%). Although some loss of sludge nutrients can occur during solid-liquid separation following bioleaching, its beneficial effects as metal removal and reduction of pathogenic bacteria are sufficient to consider the potential of this treatment before sludge disposal onto agricultural fields.

Synergy between polyaniline and OMt clay mineral in Langmuir-Blodgett films for the simultaneous detection of traces of metal ions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Origin of the heavy elements in HD 140283 Measurement of europium abundance

Context. HD 140283 is a nearby (V = 7.7) subgiant metal-poor star, extensively analysed in the literature. Although many spectra have been obtained for this star, none showed a signal-to-noise (S/N) ratio high enough to enable a very accurate derivation of abundances from weak lines. Aims. The detection of europium proves that the neutron-capture elements in this star originate in the r-process, and not in the s-process, as recently claimed in the literature. Methods. Based on the OSMARCS 1D LTE atmospheric model and with a consistent approach based on the spectrum synthesis code Turbospectrum, we measured the europium lines at 4129 angstrom and 4205 angstrom, taking into account the hyperfine structure of the transitions. The spectrum, obtained with a long exposure time of seven hours at the Canada-France-Hawaii Telescope (CFHT), has a resolving power of 81 000 and a S/N ratio of 800 at 4100 angstrom. Results. We were able to determine the abundance A(Eu) = -2.35 +/- 0.07 dex, compatible with the value predicted for the europium from the r-process. The abundance ratio [Eu/Ba] = +0.58 +/- 0.15 dex agrees with the trend observed in metal-poor stars and is also compatible with a strong r-process contribution to the origin of the neutron-capture elements in HD 140283.