Photolysis of chlorimuron‐ethyl

To examine the photostability of the herbicide chlorimuron‐ethyl (ethyl‐2‐[[[[(4‐methoxy‐6‐chloro‐pyrimidin‐2‐yl)amino]carbonyl]amino]sulfonyl]benzoate) in the field, model experiment with organic solvent was performed. Photolysis of chlorimuron‐ethyl in methanol solution resulted in the formation of seven major and five minor photoproducts, isolated and identified by spectroscopic methods. Major photoproducts reported were formed by the cleavage of sulfonylurea bridge, contraction of sulfonylurea bridge, methylation of urea nitrogen and cyclisation, whereas minor products by dechlorination.     

Photodecomposition of Isofenphos (O‐ethyl‐O(2‐isopropoxycarbonyl)‐phenyl)‐Isopropylphos‐Phoramidothioate)

Photodecomposition of the organophosphorus insecticide isofenphos (O‐ethyl‐O‐(2‐isopropoxy‐carbonyl)‐phenyl)‐N‐isopropylphosphoremidothioate) has been studied in solution, on glass and soil surfaces. Isofenphos underwent oxidation from P = S to the P = O group and deesterification on irradiation in hexane and methanol. Photoproducts were isolated and identified by spectroscopic methods.     

Photoreduction of parathion ethyl †

Photodegradation of parathion ethyl in presence of unsaturated biomolecules takes place by sufficient reduction of the phenyl nitro group. Main products are N,0‐dialkenyl hydroxylamino, cis/trans azo, and azoxy derivatives of parathion.     

New O,O‐dimethyl (2,2,2‐trichloro‐1‐carbamoyloxy)‐ethyl phosphonates and their biological activity

A series of fifteen carbamoyl derivatives of O,O‐dimethyl (2,2,2‐trichloro‐l‐hydroxy) ethyl phosphonate (trichlorphon) was synthesized. A number of them showed higher insecticidal activity, having at the same time lower toxicity than the starting biologically active structure. A waste‐free technology for the production of the more promising representatives of this series could possibly be developed in the future.     

The metabolism and distribution of [14C‐phenyl]‐ethyl parathion in a tropical soil under field conditions

The persistence, distribution and metabolism of [^l4C‐phenyl]‐ethyl parathion applied to soil columns in an agricultural farm were investigated under tropical field conditions. Volatilization, soil microbial activity, moisture levels and pH were found to influence the persistence, distribution and metabolism of this pesticide in the soil. There was rapid distribution of the pesticide in the soil matrix with time resulting in high levels of bound residues which reduced the overall rate of disappearance of parathion residues from the soil. The soil was slightly acidic but the metabolites, paraoxon, p‐nitrophenol and p‐aminophenol were detected in the soil extracts 7 days after pesticide application. After 72 days, 43.7% of the applied pesticide remained in soil composed of 18.9% extractable and 24.8% bound residues. A mechanism for the metabolism of ethyl parathion in this soil is given.     

Assesment of disinfection by‐products removal by ozonation coupled with adsorption

This research work was performed to evaluate ozonation and granular activated carbon adsorption processes from the view‐point of controlling the formation of disinfection by products (DBPs). Both the humic acid and raw water were first preozonated and then adsorbed on the activated carbon to assess the potency for removal of total organic carbon (TOC) and DBPs. The disinfection by‐product including THMs and HAAs, in principle, can be successfully removed through a use of the ozonation and granular activated carbon (GAC) adsorption processes. However, in practice dealing with the raw water, it is necessary to introduce the pilot‐plant to obtain the design and operation guidelines for the water treatment plant through the ICA (Instrumentation Control and Automation) program in our future research work.     

Charge‐transfer chromatographic study of the interaction of commercial pesticides with hydroxypropyl‐β‐cyclodextrin

The interaction between 33 commercial pesticides with hydroxypropyI‐β‐cyclodextrin (HPBCD) was studied by charge‐transfer reversed‐phase thin‐layer chromatography using aqueous sodium chloride solutions as eluents. Each pesticide interacted with HPBCD, their lipophilicity linearly decreased with increasing HPBCD concentration, the pesticide ‐ HPBCD complex (probably inclusion complex) always being more hydrophilic than the uncomplexed pesticide. In many cases the retention of pesticide increased with increasing concentration of salt in the eluent. This effect can be tentatively explained by the suppression of the dissociation of the polar groups in the solute molecules resulting in increased apparent lipophilicity. No significant correlation was found between lipophilicity and complex stability or between salting‐out effect and lipophilicity, that is other than hydrophobic forces are involved in the pesticide ‐ HPBCD interaction.     

Synthesis and antithyroid activity of 6‐n‐propyl‐5‐arylazo‐2‐thiouracils †

The synthesis of several 6‐n‐propyl‐5‐arylazo‐2‐thiouracil derivatives was achieved. The antithyroid activity of these derivatives has been determined using iodine‐125‐thiocyanate discharge technique in rats, and 6‐n‐propyl‐2‐thiouracil (PTU) as a standard. None of the 5‐arylazo‐2‐thiouracil analogs showed antithyroid activity as compared to PTU. The structure‐activity relationships (SAR) of position 5 in the PTU molecule and the requirements for better binding to the proposed receptor are discussed.     

Concentrations of polychlorinated dibenzo‐p‐dioxins and dibenzofurans in outdoor air of North‐Rhine‐Westphalia,Germany

Measurements of polychlorinated dibenzo‐p‐dioxins (PCDD) and dibenzofurans (PCDF) in outdoor air of North‐Rhine‐Westphalia were carried out. Fifty‐six samples were taken at different sites in areas of different land use and emission structures. A special filter system allowed analysis of the gas and particle phases separately. It was found that higher chlorinated PCDD/PCDF (7 or 8 chlorine atoms) are collected on glass fiber filter and lower chlorinated PCDD/PCDF (tetra‐ and penta‐CDD/CDF) are absorbed on polyurethane foam. The following isomers were determined: OCDD, OCDF and 11 isomers with chlorine substitution in 2,3,7,8‐position as well as the sum of TCDD, PeCDD, HxCDD, HpCDD, TCDF, PeCDF, HxCDF, HpCDF and the sum of PCDD (4–8) and PCDF (4–8). No 2,3,7,8‐TCDD could be detected but 2,3,7,8‐TCDF was found at 15 sites. Mean concentration in the Rhine‐Ruhr‐District for the sum of PCDD (4–8) and PCDF (4–8) was 3.2pg/m³ and 5.5pg/m³ respectively. Detection limit for TCDD and PCDD/PCDF (5–8) was 0.1–0.2 pg/m³ and 0.005–0.015 pg/m³ respectively. There is no significant indication that 2,3,7,8‐chlorinated isomers of PCDD/PCDF are predominantly decomposed by photochemical reactions in outdoor air.     

Treatment of dye‐containing wastewater by sequencing batch reactor with powdered activated carbon addition

The process involving the combination of powdered activated carbon (PAC) and biomass in the aeration basin of conventional continuous‐flow activated sludge system, known as the PACT process, has proven to be effective for treating toxic pollutants present in industrial wastewaters. In view of the many advantages of sequencing batch reactors (SBR) operationally, the objective of this study is to evaluate the PACT process under SBR operation to treat wastewater containing Acid Blue 25 (AR) and Basic Yellow 2 dyes (BR). The SBR systems were operated with FILL, REACT, SETTLE and DRAW periods in the ratio of 0.25:3.75: 1.0:1.0 for a cycle time of 6 h. The average COD and AR removal efficiencies were 89% and 93%, respectively with PAC addition compared to 76% and 7%, respectively, without PAC addition. In the case of BR, the average removal efficiencies of COD and dye increased from 52% and 9% to 90% and 93%, respectively, with PAC addition. Kinetic study conducted for the REACT period showed that both dyes exhibited a very pronounced inhibitory effect on the activities of the microorganisms. The addition of PAC was capable of reducing the inhibitory effect of only BR but not AR on the microorganisms.     

Anaerobic degradation of 4‐chlorophenol under denitrifying conditions with nitrate as the only electron acceptor

A denitrifying bacterium was isolated from activated sludge after enrichment on 4‐chlorophenol under anoxic, denitrifying conditions, and the microbial degradation of 4‐chlorophenol by this bacterium, with nitrate as the only electron acceptor, was investigated. The bacterium was capable of degrading up to 5 mM 4‐chlorophenol with stoichiometric release of chloride under denitrifying conditions. Anaerobic degradation of 4‐chlorophenol was dependent on nitrate as an electron acceptor. Nitrate (10 mM) severely inhibited the growth by the toxic effect of the accumulated nitrite. The optimum nitrate concentration for cell growth and chlorophenol degradation was 6 mM.     

Transport of metanil yellow in the rat plasma and interaction of its metabolite,p‐aminodiphenylamine with serum proteins

Binding affinity of metanil yellow and its breakdown product p‐aminodiphenylamine to serum proteins has been studied employing chromatographic separation on Sephadex G‐200 and by paper and polyacrylamide gel electrophoresis. Metanil yellow has more affinity towards albumin than to globulins. The complexing is presumably through electrostatic forces. p‐Aminodiphenylamine on the other hand, preferably binds to globulin fractions of serum protein. However, a stable binding with BSA alone was also observed. The binding was quite stable and was accompanied by a shift in absorbance from 430 nm to 500 nm. Aspartic acid moiety of protein was found to be one of the units involved in the binding of p‐ADPA to proteins.     

Toxicity of 3‐Amino‐1: 2: 4‐Triazole to Activated Sludge Biomass

3‐amino‐1: 2: 4‐triazole (AT), a potent weed killer, added to activated sludge, caused immediate and drastic reduction in oxygen uptake by biomass. AT, a known specific inhibitor of catalases of animal and plant sources, did not appreciably alter catalase of activated sludge biomass.     

Synthesis of 2,5‐diaryl‐2,4‐pentadienenitriles and their spectral,fluorescence and mutagenic properties

The condensation of substituted cinnamaldehydes and arylacetonitriles using sodium ethoxide in ethanol at room temperature afforded 2,5‐diaryl‐2,4‐pentadienenitriles in good yield. The structure of the reaction products was established on the basis of their infrared, nuclear magnetic resonance and elemental analysis data. Two representative compounds were studied for their mutagenic activity. One of them showed a weak mutagenicity while the second showed a high mutagenic activity in TA97a Salmonella strain. Both were negative in TA100. Some of these pentadienenitriles showed fluorescence in solutions.     

Multi‐phase non‐steady state equilibrium model for evaluation of environmental fate of organic chemicals

A simple mathematical fate model, Multi‐Phase Non‐Steady State Equilibrium Model (MNSEM) is proposed to evaluate distribution, persistence, and concentrations of chemicals in a model environment consisting of air, water, soil and sediment phases. The model is applied to evaluation of environmental fate and concentration of trichloroethylene and 1,4‐dichlorobenzene under generic conditions representative of Japan.

Evaluated chemical concentrations in air are within a factor of 3 of average values in Japanese atmosphere, and evaluated concentrations in water, sediment, or fish are greater than an order of magnitude below detection limits in real environments, so that evaluated concentrations are in reasonable agreement with environmental measurement data in Japan.

Although MNSEM is not a model for site‐specific evaluation of environmental fate, results suggested that this model is an adequate method to aid in evaluation of fate of chemicals under generic environment conditions. Evaluated concentration‐profiles may be used to estimate average chemical exposure concentrations for humans and the environment.     

Phototransformation of some 2‐alkyloxybenzothiazole derivatives

We have performed the photolysis of 2‐methyloxy‐, 2‐ethyloxy‐, 2‐propyloxy‐, 2‐isopropyloxy‐, 2‐(l‐methylbutyl)oxy‐, 2‐cyclohexyloxy‐ and 2‐propargyloxybenzothiazole derivatives. We have studied the influence of polarity of the solvent and presence or absence of oxygen on the course of their photochemical transformations. In general it can be concluded that the cleavage of the substituent‐oxygen bonds occurs preferentially, whereby the main product was identified in most cases to be 2‐benzothiazolinone. The rate of photolysis and the composition of the reaction mixture was dependent upon the presence or absence of oxygen. Photoreactivity of above benzo‐thiazole derivatives was also strongly dependent on the structure of the substituents in the position 2.     

Cosolvency. I. some non‐hydrogen bonding solutes with non‐hydrogen bonding solvents

The solubility data for a series of non‐hydrogen bonding, monosubstituted benzenes in binary mixtures of water and non‐hydrogen bonding cosolvents is presented. Good correlation between log solubility and fraction cosolvent is obtained, therefore the estimation of solubility in mixed solvents by a log‐linear relationship can be attained. Slight positive or negative deviations from predicted solubility values are seen at high volume fractions of cosolvents. These deviations are attributed to the cosolvent‐water interactions.     

Mass spectral studies of 6‐n‐propyl‐2‐thiouracil,its oxygen,selenium and fluorinated congeners∗

The electron ionization mass spectra of the clinically used antithyroid agent 6‐n‐propyl‐2‐thiouracil (la), its minor metabolite, 6‐n‐propyluracil (lb) and their synthetic selenium and fluorinated analogs (1c and d) have been examined. The fragmentation pattern of these thiouracil and selenouracil studied bear strong similarities with those previously derived from a study of uracil analogs. Thus, the first step in the fragmentation is a retro Diel‐Alder decomposition with the loss of HCNX (X=O, S or Se) and the production of an ion radical which undergoes further fragmentation pathways which are discussed. 6‐n‐Propyl‐2‐selenouracil (1c) did show more complicated spectra due to the six natural isotopic abundance exhibited by the selenium atom. While the fluorinated analogs (1d) did substantiate the fact that the fragmentation pattern of these derivatives proceed through fragmentation between C₂ and N₃ bond since this produces the more resonance stabilized ion.     

Leaching of arsenic from coal fly ashes 2. Arsenic pre‐leaching with sodium gluconate solution

The present study deals with the development of an efficient and reliable process for safe disposal of coal fly ash to remove arsenic that has been found to be the most easily leachable and hazardous heavy metal in coal fly ash. Pre‐leaching of fly ash prior to disposal by a natural chelating agent, sodium gluconate (SG), was proposed and studied. Several operational factors influencing arsenic leachability, such as concentration of SG solution, liquid to solid ratio, pH, length of leaching time and leaching temperature were examined. Arsenic was found to leach out substantially with SG, but almost no further release was observed from the ash pre‐leached by SG. After the pre‐leaching treatment, the desirable high buffering capacity of the ash was well sustained. SG solution was effectively regenerated by activated alumina adsorption so that it could be successfully reused for multiple leaching/adsorption cycles.     

Potentiometric studies of mixed complexes of cobalt(II) and copper(II) with l‐Asparagine and adenine

A potentiometric titration technique has been used to determine the stability constants for the various complexes of Co(II) and Cu(II) with L‐asparagine and from DNA base, e.g. adenine. Stability constants of ternary systems have been evaluated by the method suggested by Irwing‐Rossotti. In addition, the conditional constants were calculated as a function of pH. The maximum values of the conditional formation constants were found to be in accordance with the mixed‐ligand complex formation constants in a determined pH region. Furthermore, the molar fractions of different species from mixed complexes were calculated by means of formation constants. The values of stability constants of mixed‐ligand complexes at 25°C are as follows: log K= 5.25 for Co(II)‐L‐asparagine‐adenine; log K= 9.30 for Cu(II)‐L‐asparagine‐adenine. The ionic strength was kept constant at I = 0.20 with NaClO₄.