Determination of atrazine, its degradation products and metolachlor in runoff water and sediments using solid-phase extraction

In order to determine the fate of the herbicides atrazine (as well as some of its degradation products) and metolachlor in water and sediments, a method was developed to extract and analyse these compounds. The two matrices were separated completely by centrifugation followed by filtration using nylon filters (0.45 mum). Sediments were extracted with a mixture of methanol-0.1N hydrochloric acid (50:50, v/v) using a wrist-action shaker. Filtered water and extracts of sediments were adjusted to pH 4, then concentrated and purified onto two solid-phase extraction cartridges using in tandem C(18) bonded phase column atop sulfonic acid bonded column (SCX). Atrazine, deethylatrazine, deisopropylatrazine and metolachlor retained by the C(18) column were eluted with ethyl acetate. Chlorodiaminotriazine and hydroxyatrazine retained by the SCX column were eluted with a 50:50 (v/v) acetonitrile-0.1M Na(2) HPO(4) aqueous solution (pH 8.5). The extracts were quantified by high performance liquid chromatography with diode array detector (HPLC-DAD) and by gas chromatography with nitrogen-phosphorus detector (GC-NPD). Overall percent recoveries were about 75% and detection limits were between 0.05 and 0.15 microg/l., and 0.5 and 1.5 microg/kg for water and sediments, respectively.     

Interaction of atrazine with Laurentian fulvic acid: binding and hydrolysis

Ultrafiltration fractionation and liquid chromatography (LC) have been applied to the study of the binding and hydrolysis of the polar herbicide atrazine on a stoichiometrically well characterized fulvic acid. Binding requires extensive carboxylate site protonation but the binding sites represent a very small fraction of total carboxylate. The data show that binding of atrazine is not competitive with binding of the hydrolytic product hydroxyatrazine. However, smaller molecular weight fractions of the fulvic acid mixture compete with atrazine for sites on the larger molecular weight fraction. Binding equilibrium is not rapid. A model of binding involving hydrogen bonding and/or charge-transfer complexing to specific sites created dynamically by the conformational equilibria of the higher molecular weight polymeric fulvic acid fractions is proposed as the best accommodation of the variety of observed facts.     

(Benzo[4, 5]cyclohepta[l, 2-b]thiophen-4-ylidene)acetic Acids: Novel Non-ulcerogenic Antiinflammatory Agents

Compound (Z)- 8a has been found to display interesting antiinflammatory activity. In order to prepare derivatives with a wide variety of substituents in the aromatic part of the molecule, a new synthesis of the key intermediates 9a-g was developed starting from thiophene-3-carboxylic acid ( 11 ) and substituted benzyl bromides. The conversion of 9a-g to 10a-g follows a known procedure. Ketones 10a-g , on reaction with alkyl (dialkoxy-phosphoryl)acetate, followed by isomer separation and alkaline ester hydrolysis, yielded the desired derivatives (Z)- 8a-g and (E)- 8a-g . The biologically most interesting compound (Z)- 8a is currently undergoing clinical trials.     

Direct observation of the transformation of ludwigite to orthopinakiolite

Crystals with the composition Mg_1.5Mn_1.5BO₅ prepared at 1300°C in sealed platinum tubes were studied by high-resolution electron microscopy. The crystals were found to possess the ludwigite structure with very few inherent planar defects. After heating in the electron beam the electron diffraction patterns and electron micrographs showed that the ludwigite structure had rearranged to the orthopinakiolite structure. Two possible mechanisms for such a transformation have been described.     

Influence of acidification on the optical properties and molecular composition of dissolved organic matter

Acidification is a common method for preserving dissolved organic matter (DOM) in natural water samples until sophisticated laboratory analyses can be performed. However, little is known about the effects of this practice on the composition and optical properties of DOM. In this study, the effects of acidification on DOM in porewater samples collected from the RL IV bog system of the Glacial Lake Agassiz Peatlands in northern Minnesota were characterized. Molecular composition was determined by ultrahigh resolution mass spectrometry and optical properties by UV absorption and three-dimensional fluorescence spectroscopy. Excitation–emission matrix fluorescence spectroscopy results indicate that the fluorescence properties of the peatland porewater DOM were sensitive to pH and that the observed changes were fluorophore dependent. Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry revealed the appearance of newly formed, oxygen-rich compounds upon acidification. The extent to which these oxygen-rich compounds were formed was also dependent on the composition of the DOM.