Determination of fluopicolide in grapes and soil using an easy sample preparation method and gas chromatography-mass spectrometry

A simple analytical method was developed and validated to determine fluopicolide residues in grapes and soil using the “Quick, Easy, Cheap, Effective, Rugged and Safe” approach followed by gas chromatography-mass spectrometry in the selected ion monitoring mode. Fluopicolide residues were extracted from grape and soil samples with acetonitrile, and the extracts were cleaned up by dispersive solid-phase extraction with primary secondary amine sorbent. The limit of quantification was 0.02 mg kg^?1 with grape and soil samples spiked at three levels, and recoveries were from 95% to 101% and 94% to 101% with relative standard deviations from 0.2% to 4.4%. The method is less expensive and safer than existing analytical methods for grapes and soil.     

Trihalomethanes formation in water treatment plants and distribution lines: a monitoring and modeling scheme

Monitoring and modeling of the concentrations of trihalomethanes (THMs) within four water treatment plants (WTPs) and distribution lines in Fayoum City, Egypt, were studied. Sampling sites for raw and treated waters were determined by global positioning system and the Arc geographic information system software was used for mapping. THMs were monitored using 25 sampling points located at the plant exit and through the distribution lines up to the plant extremity. Results indicated that the THMs concentration varied significantly but it was very rarely higher than the allowed maximum contaminant level of 100 μg L^?1. However, at the dead zones in the distribution lines, the THMs increased by about 160% compared to in-plant level. Furthermore, the level of THMs in hot months was about 1.3 times higher than in cold ones. The influence of some independent variables such as temperature, pH, ammonia concentration, total organic carbon and color were investigated by Pearson model to find their correlation with the rate of THMs formation in WTPs. The resulted R values ranged from 0.81 to 0.98. Successful application of the model to a selected region on the distribution lines has resulted in a correlation coefficient of 0.98.     

Mercury pollution in the Sonbhadra district of Uttar Pradesh,India, and its health impacts

The Sonbhadra district in the Singrauli area of Uttar Pradesh, India, has many coal mines and thermal power plants and is a critically polluted area. Many residents of this area reported adverse health conditions which may be linked to metal pollution, especially of mercury investigated here.

In May 2012, samples of water (23), soil (7), blood, hair, and nails from persons showing adverse health conditions selected at random were collected and analyzed for total mercury by atomic absorption spectrometry.

Twenty percent drinking water samples contained mercury from 3 to 26 μg L^?1 (3–26 times the permissible limit). Soil samples had 0.5–10.1 mg kg^?1 Hg.

The average concentrations of mercury in human blood, hair, and nails were found to be 34 μg L^?1, 7.4 mg kg^?1, and 0.8 mg kg^?1, respectively. Mercury concentrations in the blood of these persons were 45 and 28 μg L^?1 on average in the case of men and women. This is much higher than the safe level of 5.8 μg L^?1 set by the United States Environmental Protection Agency (USEPA).

It was concluded that all residents of Sonbhadra sampled could be suffering from mercury toxicity as the area is polluted by Hg released from the coal-fired thermal power plants.     

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.     

Voltammetric studies of damages in DNA by mutagenic and carcinogenic alkylating chemicals

Voltammetry provides new insights into the effects exerted in vitro by methylation of native DNA. Applying single sweep voltammetry at a stationary mercury electrode the successive steps of the destabilization of alkylated DNA are investigated. The methylation of the nucleic acids is manifested by a specific electrochemical response, due to the 7‐methylguanine, a major product of the methylation of DNA. Short time effects of the methylation include the labilization of 4 to 5 base pairs per methylated guanine base. Furthermore, uncommon protonation properties of the base 7‐methylguanine‐cytosine have been detected. Long term effects of the methylation are ultimately spontaneous hydrolytic strand breaks induced by the prior depurination connected with the release of the 7‐methylguanine from the methylated DNA. A half time t_1/2 of 102 h for the depurination at 37°C has been determined. The depurination and the subsequent strand breaks alter the hydrodynamic properties of the damaged DNA, an effect which can be sensitively followed with voltammetry via the resulting changes in the diffusion coefficient of the damaged biopolymer.     

Bioconcentration of butyltin compounds by round crucian carp

Bioconcentration factors (BCF) by round crucian carp and partition coefficients between n‐octanol and water (Pow) were measured for dibutyltin, tributyltin and triphenyltin compounds. Pow was 0.97–3.66 for 7 organotin compounds. BCF of tributyltin and triphenyltin compounds was 1.70–2.77 for muscle, 1.70–2.66 for vertebra, 2.05–3.70 for liver and 1.49–3.50 for kidney.     

Genetic toxicology of metal compounds: An examination of appropriate cellular models †

Bacterial systems have not had success predicting metal carcinogenicity. Hypotheses explaining this failure are examined. Using a broad genetic endpoint, λ prophage induction, under sub‐toxic growing conditions, genotoxicity is seen for compounds of chromium, manganese, lead, molybdenum and tungsten. Copper, manganese, arsenic and molybdenum compounds enhanced UV mutagenesis in E. coli WP2.

The toxicity of metal compounds to cultured mammalian cells correlates well with rat oral LD₅₀ values. Whereas insolubility can present problems in bacterial studies, concentrations of metal compounds toxic to mammalian cells can be determined even in the presence of precipitate, and sometimes [Pb(NO₃)₂, BaCl₂ and BeCl₂] occurs only in its presence. PbS and MnS, which are insoluble, are much more toxic than the more soluble compounds Pb(NO₃)₂ and MnCl₂. These results demonstrate the importance of cellular phagocytosis of insoluble metal compounds as a factor in studying the toxicity and genotoxicity of metal compounds.     

Uptake of cadmium into cells in culture∗

Cadmium has been recognized as pollutant of the environment for many years and numerous studies on its toxic effects have been carried out. Little, however, is known about its metabolic behaviour e.g. why the metal is accumulated so extremely rapidly into the organs of men and animals. Since the study of the individual metabolic steps is very difficult in vivo cell cultures may be used to obtain first indications of what happens in the whole animal.

We used CHO cells in monolayer culture to study the conditions under which the uptake of cadmium occurs. From serumfree medium the metal is accumulated rapidly in the cells. The uptake is inhibited very strongly by the presence of serum or albumin. Accumulation occurs against a concentration gradient and is dependent on the incubation temperature. Below 10°C no cadmium uptake is seen. Several substances which are known to affect cell metabolism have been used to influence cadmium accumulation. Neither inhibitors of energy production nor microtubule or microfilament disruptors showed any substantial effect. In contrast SH‐group blocking agents markedly reduced cadmium uptake.

The results show that cadmium uptake does not occur by passive diffusion but by some active mechanism.     

Hazardous halogenated substances formed during combustion processes

The results of the emissions from combustion processes and/or from fire accidents show the risk to man and his environment and thus the need for strict legislation and critical analysis of unwanted compounds. These substances or their thermolysis products are often due to incomplete combustion or may result from the interaction of various substances.

In the following we report the formation of octachlorostyrene (OCS) and of high‐toxic substances such as polybrominated dioxins (PBrDD's), dibenzofurans (PBrDF's) by the combustion.

In order to determine a possible source of the non‐manufactured compound OCS, we conducted several model experiments in a combustion chamber at various temperatures from 400 °C to 800 °C. The thermolysis of chlorinated solvents like chloroform or of chlorinated aromatice like pentachlorobenzene produced—among other chlorinated substances—OCS as one of the major products.

Analogous combustion experiments with polyester plastics containing decabromodiphenylether as flame retardant and antimony trioxide as Synergist led to PBrDD's and PBrDF's. Here antimony trioxide seems to play an important role because in absence of this oxide, PBrDD's and PBrDF's were not found in our experimental conditions.     

Occupational exposure to airborne aromatic amines in rubber manufacturing: Determination by gas chromatography‐mass spectrometry

Aromatic amines (AAs) are used in a variety of chemical industries and consequently they are the object of great attention in occupational hygiene owing to the carcinogenic effects that many of them have shown. This work outlines a procedure for the determination of occupational exposure to airborne AAs in the rubber industry and the application of this method in a tyre manufacturing plant using p‐phenylenediamines as antiozonants. Samples were collected on a glass fibre filter followed by a silica gel tube and analyzed by GC‐MS/SIM using a capillary column coated with methyl silicone. p‐Phenylendiamines and other AAs probably formed as thermodegradation products were found in concentrations of up to 10 μg/m³ during rubber vulcanization.