Assessment of acute toxicity of ��-cyhalothrin to a freshwater catfish, Clarias batrachus

Acute static bioassays were conducted for 96 h period with λ-cyhalothrin to determine its acute toxicity to a freshwater catfish, Clarias batrachus. The 96 h LC₅₀ value was estimated to be 5.00 μg l⁻¹ (95% confidence limit: 4.114–5.712). The alterations in behavioral pattern, such as change in the color of skin, hyperactivity, loss of balance, rapid swimming, increased surfacing activity, enhanced rate of opercular activity, as well as prominent rates of convulsions in treated fish were observed with the increasing concentrations of insecticide as compared to the control fish. The results indicate that λ-cyhalothrin is highly effective even at very low concentrations.     

Comparative quantitative structure–activity relationship (QSAR) study on acute toxicity of triazole fungicides to zebrafish

We employed two-dimensional quantitative structure–activity relationship (2D-QSAR) and hologram QSAR (HQSAR) methods to quantitatively investigate the mechanism and active site of toxicity for Danio rerio exposed to triazole fungicides. Our results showed that 2D-QSAR models constructed using the energy of the lowest unoccupied molecular orbit, the net C atom charges, the octanol–water partition coefficient and the molecular shape factor had higher predictive abilities. HQSAR models containing the fragment distinctions atoms (As), bonds (Bs), chirality (Ch) and donors and acceptors (D&A) had higher reliability. It was found that 2D-QSAR results explaining the toxicity mechanism were consistent with HQSAR. In summary, the hydrophobicity and shape/size of the molecule were the important factors influencing the toxic effect of these chemicals against D. rerio. In addition, electron exchange may occur between these fungicides and the target. The study provided a method to evaluate the environmental risk of chemicals with a similar structure, based on the QSAR models obtained.     

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.     

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.     

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.     

Acute toxicity of waterborne manganese to Rutilus caspicus (Yakovlev, 1870) – gill histopathology,immune indices,oxidative condition,and saltwater resistance

The acute toxicity of manganese (Mn) in Caspian roach Rutilus caspicus was determined. The 96 h-LC₅₀ was calculated to be 300 (240–360) mg L^?1. Then, fish were exposed for 96 h to 300 (96 h-LC₅₀), 150 (50% of 96 h-LC₅₀), 60 (20% of 96 h-LC₅₀), and 0 (control group) mg L^?1 Mn. Exposure to all Mn concentrations led to fish gill damages, including epithelial lifting, hyperplasia, lamellar fusion, aneurism, and lamellar curling. Also, the fish exposed to all Mn concentrations showed decreased plasma alternative complement and lysozyme activity. Whole body superoxide dismutase, catalase, and malondialdehyde showed significant increases in the Mn-exposed fish which also exhibited lower tolerance to saltwater than the control group.     

Isomer‐specific determination and toxic evaluation of potentially hazardous coplanar PCBs,dibenzofurans and dioxins in the tissues of “Yusho” PCB poisoning victim and in the causal oil

In the light of new discoveries on the extremely toxic non‐ortho coplanar 3,3’,4,4'‐tetra‐ (T₄CB), 3,3’,4,4’,5‐penta‐(P₅CB) and 3,3'4,4’,5,5'‐hexachlorobiphenyl (H₆CB) and their mono‐ and di‐ortho analogs, tissue samples of a Yusho poisoning victim and Yusho causal oils were subjected to a thorough congener/isomer‐specific investigation for polychlorinated biphenyls (PCBs), polychlorinated dibenzofurans (PCDFs), polychlorinated dibenzo‐p‐dioxins (PCDDs). Among the many PCB congeners detected in Yusho oil, non‐ortho coplanar T₄CB constituted 3.1%, P₅CB‐0.17% and H₆CB‐0.0072% in total PCBs. Their concentrations in liver and adipose tissue were 130–700 (T₄CB), 54–720 (P₅CB) and 50–380 (H₆CB) pg/g on wet weight basis. The observed concentrations in adipose tissue were two to four fold higher than that detected in unexposed individuals. Among the PCDFs identified, toxic 2,3,7,8‐substituted isomers including 2,3,4,7,8‐P₅CDF were the dominant ones. Tetra‐ through hepta‐CDDs were detected in the oil, whereas octa‐CDD was the dominant isomer in the patient. A comparison with KC‐400 revealed enrichment of coplanar PCBs in Yusho oil along with toxic PCDFs. Enrichment was highest for 3,3'4,4'5,5'‐H₆CB followed by 3,3’,4,4'5‐P₅CB. A comparative toxic evaluation of these chemical groups in Yusho patient's adipose tissue based on “2,3,7,8‐T₄CDD Toxic Equivalent Analysis” revealed accountable toxic contribution from coplanar PCBs. This analysis also confirmed that 2,3,4,7,8‐P₅CDF was the principal causative agent in Yusho poisoning.     

Toxicity of substituted benzaldehydes to photobacterium phosphoreum and quantitative structure‐activity relationship

Acute toxicities (15min‐EC₅₀) of 21 substituted benzaldehydes to Photobacterium phosphoreum were determined. A quantitative structure‐activity relationship (QSAR) was developed using molecular connectivity indices and quantum chemical parameters, which show that the toxicity is influenced mainly by the difference of the simple and valence‐corrected fourth path molecular connectivity, polarizability, dipole moment, and the most negative net atomic charge on an atom. This study further shows that benzaldehydes are reactive chemicals, which exhibit bioreactive toxicity.     

The international toxicity equivalency factor (I‐TEF) method for estimating risks associated with exposures to complex mixtures of dioxins and related compounds∗

The International Toxicity Equivalency Factor (I‐TEF) method of risk assessment is a revised interim procedure for assessing the risks associated with exposures to complex mixtures of chlorinated dibenzo‐p‐dioxins and dibenzofurans (CDDs and CDFs). This updated scheme was developed by a working group of the North Atlantic Treaty Organization's Committee on the Challenges of Modern Society and has been officially adopted by the U.S. Environmental Protection Agency (EPA), Canada, Ontario Ministry of the Environment, the Nordic countries, the Netherlands, and the United Kingdom. Prior to the development of the I‐TEF method, at least ten slightly different schemes had been used throughout the world which complicated communication among scientists and regulatory agencies concerning the toxicological significance of complex mixtures of CDDs and CDFs. The I‐TEF approach facilitates risk communication internationally by reducing large volumes of analytical data into a single number‐International Toxicity Equivalents (I‐TEQ). As a result, the I‐TEF method represents an improvement in an already useful risk assessment/regulatory tool.     

Clinical and analytical follow‐up of 25 persons exposed accidentally to beryllium†

An accidental exposition of 25 persons to beryllium dust was used to follow up trace analytical and clinical parameters over a period of 10 months. Although no exposed person shows any symptoms of an acute beryllium intoxication, up to 5‐fold increased beryllium concentrations could be analysed in serum samples about 10 hours after exposition. The beryllium clearance shows a biological half time in the range of 2 to 8 weeks. The beryllium determination in the nanogram range was carried out using a combined method by flameless a.a.s. with a detection limit of 0.6 ppb Be and a relative standard deviation from 20 to 4% in relation to the concentration range of beryllium measurement.

Beryllium analyses are completed by thorax X‐ray, spirometry, y‐globulins and liver enzymes (SGOT, SGPT), which have shown no pathological values. Because it is known for beryllium to sensitize the cellular immune response, neopterin measurement was used to determine the activity of the immune system. Neopterin, a pteridine synthesized by activated macrophages after stimulation by gamma‐interferon derived from sensitized T‐lymphocytes, was determined in urine samples by HPLC combined with an fluorescence detector. Only in two cases a slight increase of neopterin has been found. As a result of this study it can be summarized, that a short‐time exposure to beryllium (10–20 h), which results in a increase of beryllium in serum to the fivefold normal beryllium level, does not initiate any symptoms of an acute beryllium intoxication. The exposed persons are controlled in future to evaluate the further course.     

Crystallization and X‐ray structure of 3,3’,4‐trichlorobiphenyl (PCB 35)∗

A method for the preparation of single crystals of PCB 35 suitable for single crystal X‐ray structure determination was developed. This method has already been proven suitable for 2,4'‐dichlorobiphenyl and may prove useful for other PCBs or related compounds. The crystals of PCB 35 are orthorhombic, spacegroup P2₁22₁ (a= 10.665(8), 6 = 3.825(3), c= 14.086(9) Å) and the structure was refined to R = 0.094 for 156 unique observed reflections and 43 parameters. Although the crystals were of poor quality, the structure determination unequivocally confirmed the substitution pattern of the biphenyl moiety by Cl atoms inferred previously from spectroscopic methods. The dihedral angle between the planes of the two phenyl rings is 33(2)°.     

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/Fs) in dated environmental samples,and their connection to known sources

This article investigates available environmental data from measurements of the everywhere present contaminants polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) in dated trends in sediment, soil and herbage from locales in Europe and North America. The PCDD/F data are examined in relation to potential major PCDD/F sources based on volume: wood and coal, example of natural combustion; pentachlorophenol (PnCP), example of chlorinated aro‐matics; and polyvinyl chloride (PVC) pyrolysis, example of chlorinated aliphatic. Collected PCDD/F data of congener sums and 2, 3, 7, 8‐substituted congener (PCDD/F profiles) have been investigated with multivariate methods: principal component analysis (PCA) and partial least squares projection to latent structures model (PLS). The results show that PCDD/F data from 12 locales can be separated in one to three independent profiles. Normally one profile is related to the PCDD/F found in PnCP and another to combustion. A subtype of the ‘PnCP’ and ‘combustion’ profiles indicates PCDD/F contributions from PVC‐related combustions. The environmental profiles exhibit some differences from the suggested sources. The relatively unprotected PCDD/F related to PnCP is suggested to have passed photolytic and/or thermal dechlorinations. Lower‐chlorinated congeners in environmental profiles related to combustion appear to have been influenced by environmental distribution processes. PCDD/F data before industrial production of chlorinated organics have only limited similarity to PCDD/F in technical PnCP profiles; an average 4.6% of the PCDD/F is related to PnCP. This suggests that PnCP similarity in recent deposition profiles cannot be a result of environmental transformation. The average proportion of PnCP‐related PCDD/F profile in recent depositions is 35% with North America high (average 57%) and Europe low (average 24%).     

Synthesis,separation and structure determination of 2,3,3'‐trichlorobiphenyl (PCB 20)† and 3,3’,4‐trichlorobiphenyl (PCB35)†

The combined synthesis and spectrometric characterization of 2,3,3'‐trichlorobiphenyl (PCB 20) and 3,3’,4‐trichlorobiphenyl (PCB 35) is described for the first time. By a combination of highly efficient column distillation and repeated recrystallizations it was possible to isolate the two products as reference materials with a purity exceeding 99%. X‐ray analysis of crystals of 2,3,3'‐trichlorobiphenyl positively identified the substitution pattern of the biphenyl moiety by chlorine atoms. The two phenyl rings are at an angle of 52°, while the relative disposition of the chlorine atoms on both rings is closer to anti than to syn.     

Antimutagenic and bacteriostatic activities of Schiff‐base compounds derived from aminoguanidine,semicarbazone and thiosemicarbazone and a copper(II)‐coordination complex

The Schiff‐base aminoguanidine compounds including a resorcylidene aminoguanidine copper(II) complex that were synthesized at our laboratory posses non‐mutagenic properties when tested with Ames test using Salmonella typhimurium TA97, TA100 and TA102 bacterial strains. These compounds were tested as possible pharmacological agents in preventing a wide array of illnesses. Additionally, some of these compounds exhibit strong antimutagenic and bacteriostatic activity. Nitrovin, a known mutagen, was used in the antimutagenicity tests as the inducer. A three‐dimensional projection of the copper(II) complex was derived by the semi‐empirical method ZINDO/1 to obtain additional information about its structure, and to help elucidate a possible mechanism of action.     

Relationships between octan‐1‐ol/water partition coefficients,aqueous activity coefficients and reversed phase HPLC capacity factors of alkylbenzenes,chlorobenzenes, chloronaphthalenes and chlorobiphenyls

Linear relationships between logarithms of octan‐1‐ol/water partition coefficients (K_d,oct), aqueous activity coefficients (y_aq) and extrapolated RP HPLC capacity factors (k‘_w) are found for four types of aromatic hydrocarbons (alkylbenzenes and poly‐chlorinated benzenes, ‐naphthalenes and ‐biphenyls).

Both log K,_d,oct and logk‘_w increase with the increasing number of chlorine or methyl‐ene substituents. These increases of log K,_d,oct and log k‘_w are proportional and almost independent of the parent compound. In addition, these increases are linear to increases of logy_aq. The slopes of logk‘_w‐logy_aq and log K,_d,oct‐logv_aq relationships deviate significantly from 1.0. This suggests that the activity coefficients of the test compounds in both octan‐1‐ol and in the stationary phase of the RP column increase after substitution of aromatic compounds with methylene or chlorine.     

Do we need to examine the quantitative data obtained from toxicity studies for both normality and homogeneity of variance?

Most of the statistical techniques used to evaluate the data obtained from toxicity studies are based on the assumption that the data show a normal distribution and homogeneity of variance. Literature review on toxicity studies on laboratory animals reveals that in most of the cases homogeneity of variance alone is examined for the data obtained from these studies. But the data that show homogeneity of variance need not always show a normal distribution. In fact, most of the data derived from toxicity studies, including hematological and biochemical parameters show a non-normal distribution. On examining normality of data obtained from various toxicity studies using different normality tests, we observed that Shapiro-Wilk test is more appropriate than Kolmogorov-Smimov test, Lilliefors test, the normal probability paper analysis and Chi square test. But there are situations, especially in the long-term toxicity studies, where normality is not shown by one or more than one of the dosage groups. In this situation, we propose that the data maybe analyzed using Dunnett multiple comparison test after excluding the data of the groups that do not show normality However, the biological relevance of the excluded data has to be carefully scrutinized. We also observed that the tendency of the data to show a normal distribution seems to be related to the age of the animals. Present paper describes various tests commonly used to test normality and their power, and also emphasizes the need of subjecting the data obtained from toxicity studies to both normality and homogeneity tests. A flow chart suggesting the statistical techniques that maybe used for both the types of data showing a normal or non-normal distribution is also proposed.     

Effects of lead and selected pyrethroids/piperonyl butoxide alone and in combination on Na,K‐ATPase

In vitro effects of Pb²⁺, the pyrethroid insecticides cypermethrin, fenvalerate and the syner‐gist piperonyl butoxide on sodium‐potassium‐activated adenosine triphosphatase (Na,K‐ATPase) from dog kidney were determined. Pb²⁺ with an estimated IC50 value of 5.2 μM was found to be a potent inhibitor of Na,K‐ATPase activity, whereas Na,K‐ATPase was less sensitive to the pyrethroids tested and piperonyl butoxide. Investigation with circular dichroism (CD) spec‐troscopy showed that inhibition occurs through conformational changes of the α‐subunit of the enzyme. The kinetic characteristics of inhibition of Na,K‐ATPase with varying substrate (ATP) concentrations as well as with varying Na⁺ concentrations exhibited a competitive type of inhibition with Pb²⁺ in the μM range. With Pb²⁺ alone in the enzyme assay no conformational changes of the protein could be observed which confirmed the assumption that Pb²⁺ can bind to the Na⁺ binding site of the α‐subunit. Uncompetitive type of inhibition occurred with varied K⁺ concentrations demonstrating that this cation binding site is not affected directly by Pb²⁺.

Complete reversal of Pb²⁺ by DTT confirms that a possible target for interaction of this heavy metal ion with Na, K‐ATPase are specific SH groups.

Synergistic effects could only be determined with higher Pb²⁺ concentrations of 3, 5 and 7 μM plus piperonyl butoxide while all other combinations with this heavy metal plus organic substances where of the additive type. With CD spectroscopy also only additive effects were observed. These results demonstrate that higher concentrations of piperonyl butoxide favor the binding of Pb²⁺ to the Na⁺ binding site by conformational changes of the protein.     

Residues of 14C‐γ‐HCH in paddy after dusting,and the fate of γ‐HCH during refining process of rice bran oil

Paddy (rice) plants were dusted with 10% HCH containing ¹⁴C‐Γ‐HCH, at the rate of 2.5 kg a.i./ha and ¹⁴C‐residues were determined in different fractions of rice. Rice bran (0.187 ppm) had more of ¹⁴C‐residues than grain (0.026 ppm) and husk (0.042 ppm). The rice bran oil contained 0.129 ppm HCH residues. While degumming, dewaxing, alkali refining and bleaching had no effect, deodorisation alone eliminated 99.5% of added ¹⁴C‐residues in rice bran the oil during refining process.     

Determination of phenol,cresols and xylenols in workplace air using XAD‐2 sorbent cartridges

A method for sampling and analysis of phenolic compounds in workplace atmospheres using Amberlite XAD‐2 sorbent tubes has been laboratory and field tested. After extraction of the adsorbed phenols with methylene chloride, the concentrated extract was analyzed by capillary column gas chromatography coupled with a flame ionization detector or a mass spectrometer. For a 3L air sample, the method has a detection limit for phenol, cresols, alkyl‐substituted phenols and xylenols of 0.3 mg/m³ using gas chromatography with flame ionization detection (GC/FID) analysis and 0.07 mg/m³ using gas chromatography mass spectroscopy/selected ion monitoring GC‐MS/SIM. Evaluation tests conducted in the laboratory indicated recoveries >85% for a wide range of phenols, cresols, xylenols and other alkyl‐substituted phenols and resorcinol. Sampling conditions were established to ensure that no breakthrough occurred for a predetermined sample volume of three (3) liters even in humid atmospheres. Stability tests indicated that for storage of up to 2 weeks at 4°C, only resorcinol showed a significant reduction in sample recovery. The proposed method and NIOSH Method 3502 were compared for the determination of phenol concentrations in air samples collected at a plant processing phenolic resins. Phenol was positively identified in the XAD sample using GC‐MS/SIM and was detected at concentrations of 40–50% of the total phenols detected using NIOSH Method 3502. This difference is attributed to the airborne paniculate matter which is known to contain bisphenols that will contribute to the total phenolic content sampled in Method 3502, but not on the XAD sample.