On-line preconcentration of inorganic mercury and methylmercury in sea-water by sorbent-extraction and total mercury determination by cold vapour atomic absorption spectrometry

A comparative study of three mercury chelate forming reagents [diethyldithiocarbamate, pyrrolidin-1-yldithioformate and diphenylthiocarbazone (dithizone)] has been carried out for the preconcentration of ultratrace amounts of inorganic mercury and methylmercury in silica C(18) minicolumns as the solid sorbent. Sample flow injection in-line sorbent extraction was coupled with continuous cold vapour atomic absorption spectrometry (CVAAS) for detection. Results showed the superiority of the carbamate type reagents over the dithizone for the on-line formation and preconcentration of the corresponding mercury chelates. Using diethyldithiocarbamate (DDC) as reagent, aqueous sample volumes of 100 ml can be preconcentrated with 100% efficiency for both inorganic mercury and methylmercury. Quantitative release of the retained DDC chelates was obtained for volumes of eluent (ethanol) of 50 microl. Following the proposed procedure, detection limits of 16 ng/l. of mercury were achieved for sample volumes of 25 ml. The relative standard deviation was +/- 3.4% at 0.5 microg/l. Hg(II) levels. The method has been successfully applied to the determination of low levels of mercury in sea-water.     

Determination of lead in wines by hydride generation atomic absorption spectrometry.

The optimization of lead hydride generation in aqueous ethanolic media and the influence on its generation of the wine components, both white and red, have been studied. These interferences were overcome by careful control of the parameters affecting hydride generation and the procedure was applied to the determination of Pb in wines. The method is fast, accurate and sensitive and can be used to quantify 24 ppb of Pb in wines.     

Diphosphacarbollide analogues of the C5H5- anion: isolation of the nido-di- and triphosphacarboranes 7,8,9-P2CB8H10, [7,8,9-P2CB8H9]-, [7,8,10-P2CB8H9]-, and 7,8,9,10-P3CB7H8

Treatment of a solution of excess PCl(3) and PS (PS = "proton sponge" = 1,8-dimethylamino naphthalene) with arachno-4-CB(8)H(14) (1) in CH(2)Cl(2), followed by hydrolysis of the reaction mixture, resulted in the isolation of the eleven-vertex diphosphacarbaborane nido-7,8,9-P(2)CB(8)H(10) (2) (yield 34%) as the main product. Other products isolated from this reaction were the phosphacarboranes nido-7,8,9,10-P(3)CB(7)H(8) (3) (yield 5%) and closo-2,1-PCB(8)H(9) (4) (yield 15%). Compound 2 can be deprotonated by PS in CH(2)Cl(2) or NaH in diethyl ether to give the [nido-7,8,9-P(2)CB(8)H(9)](-) (2(-)()) anion, which gives back the original compound, 2, upon re-protonation. Thermal rearrangement of anion 2(-) (Na(+) salt) at 350 degrees C for 2 h produced the isomeric [nido-7,8,10-P(2)CB(8)H(9)](-) (5(-)()) anion, which was isolated as a PPh(4)(+) salt (yield 86%). Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B] COSY, (1)H{(11)B(selective)}, (1)H{(31)P(selective)}, and gradient-enhanced ([(1)H-(13)C] HSQC) magnetic resonance measurements led to complete assignments of all resonances which are in excellent agreement with the structures proposed. Coupling constants, (1)J((31)P,(13)C), (2)J((31)P,C,(1)H), and (1)J((31)P,(31)P), were calculated using the DFT method B3LYP/6-311+G(d,p). The molecular geometries of all compounds were optimized ab initio at a correlated level of theory (RMP2(fc)) using the 6-31G basis set, and their correctness was assessed by comparison of the experimental (11)B and (13)C chemical shifts with those calculated by the GIAO-SCF/II//RMP2(fc)/6-31G method. The computations also include the structures and chemical shieldings of the still unknown isomers [nido-7,10,8-P(2)CB(8)H(9)](-) (6(-)) and [nido-7,9,8-P(2)CB(8)H(9)](-) (7(-)).     

1,5-bis(dicarboxymethylaminomethyl)-2,6- dihydroxynaphthalene as a selective spectrofluorimetric reagent for calcium

1,5-Bis(dicarboxymethylaminomethyl)-2,6-dihydroxynaphthalene (BDDN) forms fluorescent complexes with aluminium, barium, beryllium, calcium, magnesium and strontium. All the complexes have 2:1 metal :ligand ratios. Barium, calcium, magnesium and strontium exhibit maximal fluorescence at pH 11.7, with excitation and emission maxima at 385 and 445 nm respectively. Aluminium and beryllium show maximal fluorescence at pH 5.8 and 5.2 respectively, the excitation and emission maxima being at 370 and 405 nm. The formation of the calcium complex provides a highly sensitive and selective determination of calcium in the range 10/2-500 ng. The fluorescence measurement of calcium should be made within 5 min of mixing the solutions because of the instability of the reagent at the given pH. Potassium cyanide may be used as a masking agent and ter- or quadrivalent cations should be removed by preliminary extraction with 8-hydroxyquinoline in chloroform at pH 6.0. In such conditions, of 33 cations studied, only magnesium (>20 ng), strontium (>70 ng) and barium (>150 ng) caused interference in the determination of 300 ng of calcium. Among 16 anions examined, only EDTA interfered seriously.     

Field alpha-spectroscopy of radon (<Superscript>222</Superscript>Rn) and actinon (<Superscript>219</Superscript>Rn) progeny in soil gas: Locating a radon source

Summary The activities of²¹⁸Po,²¹⁴Po and²¹¹Bi were determined in samples obtained of soil/gas. Sampling work was taken in Jáchymov (Czech Republic) at the outcrop of the Geister-vein,by electrostatic precipitation from filtered soil gas on stainless steel disks.The samples were measured in a field laboratory using a semi-conductor alpha-spectrometer.The activities of²¹⁸Po,²¹⁴Po and²¹¹Bi were calculated.Samples taken from active dump material (near-by radon source) exhibited a high²¹¹Bi/²¹⁴Po ratio, while those of the vein outcrop (a relatively deeper source) had a low ratio.A mathematical model was employed to determine the radon age calculated from the actinon/radon input ratio.This varied in a range of 5.6 to -7.7 seconds.Negative age values are probably caused by the preference for actinon, which rapidly comes into equilibrium with the source of this gas.     

Transfer reaction of the polystyrene radical with electron-acceptor molecules of tetrachlorophthalanhydride

The transfer constants (C_s) of the polystyrene radical with some derivatives of phthalic acid have been determined. Among the agents used, tetrachlorophthalanhydride (TCPA) differs distinctly from other compounds by its value of C_s 3·1 × 10^?3 for thermal and 3·4 × 10^?3 for initiated polymerization of styrene. The values of C_s for phthalanhydride, dimethyl phthalate, and tetrachlorodimethyl phthalate are lower by two decimal orders. The considerable decrease in the degree of polymerization of styrene prepared in the presence of TCPA is mainly attributed to the increased reactivity of chlorine atoms in TCPA induced by the acceptor effect of anhydride ring. Participation of a TCPA-styrene complex in transfer reaction has been assumed but not proved.     

Polychlorinated polyamides—III. Synthesis and characterization of polyamides derived from perchloroterephthaloyl dichloride

Six new polyamides have been prepared either by polymerization in solution or by interfacial polymerization by reacting perchloroterephthaloyl dichloride with aromatic diamines. The polymers were characterized by i.r. spectroscopy, elemental analysis, DSC, and TGA. The glass transition temperature, the melting temperature, and the thermal decomposition temperature have been determined. In order to estimate the molecular weights, intrinsic viscosities were determined. Some of the polymers showed high thermal stability.     

Synthesis,characterization and a thermogravimetric study of copper,cobalt and tin mono- and bis-adducts with ethyleneurea,ethylenethiourea and propyleneurea

This paper describes the synthesis, characterization and a thermogravimetric (t.g.) study of 11 adducts of general formula MCl₂·nL (M = Cu, Co and Sn; n = 1 and 2 for Sn, and 2 for Cu and Co; L = ethyleneurea eu, ethylenethiourea etu, and propyleneurea pu). The i.r. results shows that the eu and pu adducts are coordinated through oxygen, whereas for etu nitrogen is the coordination site. The (C=O) or (C=S) trend is: Cu > Co > Sn. The t.g. curves show that the adducts release ligand molecules in a single mass loss step. As regards considering adducts with the same stoichiometry, the observed thermal stability trend is: etu > pu > eu.