Speciation of selenium in groundwater: seasonal variations and redox transformations.

Speciation of selenium in groundwater is essential from the viewpoint of toxicity to organisms and biogeochemical cycling. Selenium speciation in groundwater is controlled by aquifer redox conditions, microbial transformations, dissolved oxygen (DO) and other redox couples. A suburban area of Chennai city in India, where improper waste disposal measures have been practiced is selected for this study. Se(IV), Se(VI) and other hydrochemical parameters were monitored in shallow ground water during pre- and post-monsoon seasons for a period of three years. The objective of the study was to investigate the effect of groundwater recharge on selenium speciation. The concentration of Se(IV), and Se(VI) ranged between 0.15-0.43 µg L(-1) and 0.16-4.73 µg L(-1), respectively. During post-monsoon period the concentration of Se(IV), and Se(VI) ranged between 0.15-1.25 µg L(-1) and 0.58-10.37 µg L(-1), respectively. Se(VI) was the dominant species of selenium during the pre- and post-monsoon periods. During the post-monsoon periods, leaching of selenium from soil was more effective due to the increased oxidizing nature of the groundwater as indicated by the DO and redox potential (Eh) measurements. This finding has important implications on the behavior of selenium in groundwater, and also on the health of people consuming groundwater from seleniferous areas.

Chromium speciation in groundwater of a tannery polluted area of Chennai City, India.

Chromium speciation in groundwater of a tannery polluted area was investigated for the distribution of chromium species and the influence of redox couples such as Fe(III)/Fe(II) and Mn(IV)/Mn(II). Speciation analysis was carried out by ammonium pyrolidinedithiocarbamate (APDC)-methylisobutylketone (MIBK) procedure. The groundwater samples were analyzed for Cr(III), Cr(VI), and Cr(III)-organic complexes. The APDC could not extract the Cr(III)-organic complexes, but HNO3 digestion of the groundwater samples released the Cr(III)-organic complexes. The groundwater of the area is relatively oxidizing with redox potential (Eh) and dissolved oxygen (DO) ranged between 65 and 299 mV and 0.25 and 4.65 mg L(-1), respectively. The Fe(II) reduction of Cr(VI) was observed in some wells, but several wells that had Fe(II)/Cr(VI) concentrations more than the stoichiometric ratio (3:1) of the reduction reaction also had appreciable concentration of Cr(VI). This could partly be due to the oxidation of Fe(II) to Fe(III) by DO. It appears that the occurrence of Mn more than the Fe(II) concentration was also responsible for the presence of Cr(VI). Other reasons could be the Fe(II) complexation by organic ligands and the loss of reducing capacity of Fe(II) due to aquifer materials, but could not be established in this study.

Factor analysis and linear regression model (LRM) of metal speciation and physico-chemical characters of groundwater samples.

An approach is described for viewing the interrelationship between different variables and also tracing the sources of pollution of groundwater of north Chennai (India). The data set of 43 variables which include major ions, minor ions and trace metal speciation (Cu, Pb, Cd and Zn) collected during the pre-monsoon and post-monsoon seasons of the year 2000-2001, was subjected to R-mode factor analysis to comprehend the distribution pattern of the said variables. It was found that first factor measures salinity and hardness which explained 19.12% of the total variance (comprised of variables EC, TDS, Na+, K+, Ca2+, Mg2+, total hardness, Cl- and SO4(2-)) during pre-monsoon, while it was 25.08% during post-monsoon. The second and third factors were attributed to speciation of zinc and copper ions during both pre-monsoon and post-monsoon. Although there were two more factors, loaded with speciation parameters of lead and cadmium, the variance of them were less than 10%. From this study it is seen that sea water intrusion, municipal solid waste disposal are the identified sources of component of pollution. The importance of metal ions is taking a secondary role and the anthropogenic origin-industrial activity, is the reason in the evaluation of pollution status as they come in the second, third, fourth and fifth factors. As the trace metal speciation was grouped in separate factors, linear regression model (LRM) with correlation analysis was applied to check its validity for prediction of speciation and to apply LRM for rapid monitoring of water pollution.

Mechanism of volatile hydride formation and their atomization in hydride generation atomic absorption spectrometry.

The mechanism of volatile hydride generation (HG) and the formation of analyte atoms in the quartz cell atomizer used in the determination of hydride-forming elements (As, Bi, Ge, Pb, Sb, Sn, Te etc.) by atomic absorption spectrometry (AAS), have been critically reviewed. The nascent hydrogen mechanism failed to explain hydride generation under different experimental conditions when tetrahydroborate (THB), amineboreanes (AB) and cyanotrihydroborate (CBH) were used as reductants. Various experimental evidence suggested a non-nascent hydrogen mechanism, in which the transfer of hydrogen directly bonded to boron to an analyte takes place. In electrochemical hydride generation (EcHG), the reduction of the analyte species and subsequent hydrogenation was proposed. The mechanism of analyte atom formation in a quartz tube atomizer has been explained by the following hypotheses: thermal decomposition, oxidation by 02 and collisions by hydrogen free radicals. The free-radical mechanism satisfactorily explains most of the analytical implications. The significant variation in the experimental conditions required to generate different analyte hydrides makes it difficult to arrive at a generalized mechanism of hydride formation.

Indirect potentiometric titration of sulphamethoxazole in the presence of trimethoprim in co-trimazole tablets using copper based mercury film electrode.

A simple and rapid indirect potentiometric titration of sulphamethoxazole in the presence of trimethoprim contained in co-trimazole tablets is described. The method is based on the formation of a complex of sulphamethoxazole with a known excess of silver ions and the titration of unreacted silver ion potentiometrically using an inexpensive lab-made copper based mercury film electrode (CBMFE). The titration conditions have been optimized for the determination of 1.0-10.0 mg of sulphamethoxazole in pure and dosage forms. The precision and accuracy of the method have been assessed by the application of lack of fit test and other statistical methods. Overall mean recovery and relative standard deviations obtained were 99.88% and 1.32% (n=7) respectively. No interference was caused by other excipients present in pharmaceutical dosage forms. The application of this method for sulphamethoxazole assay in the presence of trimethoprim in tablets was validated by the comparison of results obtained by the proposed method with that of the British Pharmacopoeia (BP) method using F- and t-statistical tests of significance.

Biacetyl monoxime glycinimine as a selective reagent for palladium and nickel.

Biacetyl monoxime glycinimine is proposed as a new reagent for the selective gravimetric and extractive photometric determination of Pd(II) and Ni(II). The reagent forms yellow and rose-red water-insoluble complexes with Pd (pH 0.5-5.5) and Ni (pH 5.0-11.2) respectively. The complexes can be used for direct gravimetric determination or extracted with molten naphthalene. The solidified naphthalene-complex mixture is dissolved in chloroform and measured photometrically. The effects of experimental variables and diverse ions are reported. The proposed reagent offers better selectivity than dimethylglyoxime.