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.     

Quantitative structure–activity relationship methods for the prediction of the toxicity of pollutants

Environmental Chemistry Letters - Continuous flow of toxic and persistent compounds to the environment is a global health issue. However, assessing the toxic effects of compounds...     

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.     

Investigation of the hemolytic effects of various organophosphoric acid triesters (OPEs) and their structure‐activity relationship

The hemolytic effects of various organophosphonc acid triesters (OPEs) were investigated and they showed strong hemolyic toxicity except triethyl phosphate and tris(chloroethyl)phosphate. 2‐Ethylhexyl diphenyl phosphate (EHDP) showed the strongest toxicity. By quantitative structure‐activity relationship (QSAR) study, one‐parameter regression equation to estimate hemolysis was not obtained. But, two‐parameter regression equations were obtained which were enought to estimate EC₅₀ and EC₂₀. The correlation coefficients with the two‐parameter regression equations were 0.939 for log(l/EC₅₀) and 0.946 for log(l/EC₂₀).     

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.     

Alkylation of metals and the activity of metal‐alkyls†

The biochemical basis for resistance to metal ion toxicity is emerging though it is complicated by the different resistance mechanisms. Several strategies for resistance to toxic metal ions have been identified:

1. The development of energy driven efflux pumps which keep toxic element levels low in the interior of the cell. Such mechanisms have been described for Cd(II) and As(V).

2. Oxidation (e.g. AsO^2‐ to AsO₄ ^3‐) or reduction (e.g. Hg²⁺ to Hg⁰) can enzymatically and intracellularly convert a more toxic form of an element to a less toxic form.

3. The biosynthesis of intracellular polymers which serve as traps for the removal of metal ions from solution such as traps have been described for cadmium, calcium, nickel and copper.

4. The binding of metal ions to cell surfaces.

5. The precipitation of insoluble metal complexes (e.g. metal sulfides and metal oxides) at cell surfaces.

6. Biomethylation and transport through cell‐membranes by diffusion controlled processes.

In this short review I shall discuss the implications of biomethylation as a detoxification mechanism for microorganisms as well as for certain higher organisms.     

The relation between chemical structure and mutagenic activity of some polycyclic aromatic sulfur heterocycles (s‐pah)

Results of Hückel Molecular Orbital (HMO) calculations strongly suggest identical metabolic activation routes for the mutagen benzo[2,3]phenanthro[4,5‐bcd]thiophene and its homocyclic parent, benzo[a]pyrene.     

Metal binding capacity of soft acid,organic‐rich waters

Organic carbon from one stream and two ponds in South Carolina was fractionated into five nominal molecular diameter fractions by ultrafiltration. The concentrations associated with and binding capacity for Ca, Cd, Cu and Pb were determined for each fraction. The distribution of organic carbon among ultrafilter fractions varied from water to water, with the largest percentage occurring in the smaller fractions. Calcium was associated with each of the fractions isolated from each of the three waters, indicating Ca is bound to organics in all fractions, however, more than 99% of the Ca which passed the smallest ultrafilter was removed by cationic exchange resin. Each fraction bound more Ca than Cd, Cu or Pb except in a few cases where Pb binding was greater. All of the organic fractions had their Ca++ binding sites saturated. Calcium was not an effective competitive ion against Cd, Cu or Pb for organic binding sites. The total Cu binding capacity was less than that of Ca or Pb but similar to that of Cd. Naturally occurring organics bound more Pb than Cd or Cu but less than Ca. Saturation of Cu binding sites was less than 20% in most ultrafilter fractions except that with a nominal molecular weight of between 10,000 and 300,000 where the percent of saturation was as much as 60%. Approximately 50% of the Cu was removed onto anionic exchange resin in two waters while more than 90% was removed from water with a high organic content. Percent saturation of Cd and Pb binding sites ranged from 0.091% to 5.4% and 0.059% to 1.5%, respectively. All ions tested effectively competed with Cd, Cu or Pb for some but not all binding sites, indicating that organic binding sites were heterogeneous. A generalized order of metal‐organic stabilities based on competition for binding sites is Al>Cd>Pb>Cu>Ni = Mg=Zn = Mn>Ca. Both Cd+2 and Al+3 effectively out competed Pb++ and Cd and Pb out competed Cu for most organic binding sites.     

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.     

Mutagenic activity of transition‐metal complexes: Relation structure‐mutagenic and antibacterial activity for some Pd(II), Pt(II) and Rh(I) complexes†

The inhibitory and mutagenic action of some Pd(II), Pt(II) and Rh(I) complexes towards various bacterial strains has been evaluated, and some correlations have been found between the chemical behaviour of the complexes and their selective biological activity: most of the complexes cause only a DNA damage repaired by the excision repair system. Particularly, the Rh(I) complexes used in this work show selective antibacterial effects on defective but no effect on wild‐type strains.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part IV†: Incorporation of inorganic chlorine into organic matter and thermochemical aromatizations

The pyrolysis and chlorination of petroleum coke in a NaCl‐KCl melt results in the production of CCl₄ and C₆Cl₆. Polychlorinated dibenzo‐p‐dioxins (PCDDs) are produced from the air oxidation and chlorination of coal using HCl or Cl₂. Smoking of tobacco containing ³⁶Cl^e provides CH₃ ³⁶Cl.

At 350°C, the rateof aromatization of 1,3‐cyclohexadiene is negligible as compared to that of 1,4‐cyclohexadiene. The aromatization of the latter diene proceeds through the molecular elimination of hydrogen; while that of 1,3‐cyclohexadiene expecially at higher pressure (10–90 Torr) and at 362–421 °C involves free radical chain mechanism.     

Effects of the Ellagic acid on the N‐Acetyltransferase activity and Acetylation of 2‐aminofluorene in the rat

The effects of the ellagic acid on the in vitro and in vivo acetylation of 2‐aminofluorene were investigated in male Sprague‐Dawley rats. For in vitro examination, cytosols with or without ellagic acid co‐treatment showed different percentage of 2‐aminofluorene acetylation. For in vivo examination, pre‐treatment of male rats with ellagic acid (10 mg/kg) 24h prior to the administration of 2‐aminofluorene (50 mg/kg) resulted in a 26% and 29%, respectively, decrease in the urinary and fecal recovery of N‐acetyl‐2‐aminofluorene, and a 37% decrease in the metabolic clearance of 2‐aminofluorene to N‐acetyl‐2‐aminofluorene. This is the first demonstration that ellagic acid decrease the N‐acetylation of carcinogens in vitro and in vivo.     

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)°.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins part III†: Thermodegradation of organometallics and polymers

Thermodegradation of organometallics viz. RMX (where M = Mg, Ti, Pd, Sn, Si, Al; and X =halogen atom) provides corresponding haloorganics i.e. RX. 1,2‐Shifts of H and Cl on the carbene species like CH₂F. CF and CFCL₂, CF produced from R. CF. Si F₃ (R = CH₂F, CFCl₂) are preferred to that of fluorine. The thermolysis of R.CF₂. Si Cl₃ (R = CH₂F) produces chloroolefins via halogen exchange. Major products of thermal degradation of poly (vinyl chloride) (PVC) are HCl and benzene but the mechanism of PVC thermodegradation is still a matter of dispute. The thermal cracking of lignins yields substituted phenols.     

Quantitative characterization of Cu binding potential of dissolved organic matter （DOM） in sediment from Taihu Lake using multiple techniques

Dissolved organic matter （DOM） plays an important role in heavy metal speciation and distribution in the aquatic environment especially for eutrophic lakes which have higher DOM concentration. Taihu Lake is the third largest freshwater and a high eutrophic lake in the downstream of the Yangtze River, China. In the lake, frequent breakout of algae blooms greatly increased the concentration of different organic matters in the lake sediment. In this study, sediment samples were collected from various part of Taihu Lake to explore the spatial difference in the binding potential of DOM with Cu. The titration experiment was adopted to quantitatively characterize the interaction between Cu（II） and DOM extracted from Taihu Lake sediments using ion selective electrode （ISE） and fluorescence quenching technology. The ISE results showed that the exogenous DOM had higher binding ability than endogenous DOM, and DOM derived from aquatic macrophytes had a higher binding ability than that derived from algae. The fluorescence quenching results indicated that humic substances played a key role in the complexation between DOM and Cu（II） in the lake. However, because of the frequent breakout of algae blooms, protein-like matters are also main component like hnmic matters in Taihu Lake. Therefore, the metals bound by protein-like substances should be caused concern as protein-like substances in DOM were unstable and they will release bound metal when decomposed.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part V†: Hypotheses and summary

The hypotheses on the de novo syntheses of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo‐p‐dioxins (PCDDs), based on known literature, are presented. Polychlorinated benzenes and polychlorinated phenols are probably key intermediates.

In the present article, hypotheses that may account for the presence of polychlorinated dibenzofurans (PCDFs) and dibenzo‐p‐dioxins (PCDDs) in the effluents from municipal and industrial incinerators are put forward. These hypotheses are based on the previously surveyed literature (Ref. 203–206) and experimental results on laboratory scale and thermodynamic calculations are considered. The interconnections of various reaction steps are speculative and no technological information was added to account for conditions in real incinerators. Conclusion of the discussions on the related subject matter, presented in the Parts I‐IV (Ref. 203–206), are also described in this paper.     

Cytotoxic activity of spark‐decomposed sulfur hexafluoride and analysis of cytotoxic contributions of individual spark decomposition products†

Sulfur hexafluoride decomposed by electrical sparks has been found to by cytotoxic to hamster cells when tested in an in vitro cell survival assay, while SF₆ shows no cytotoxic activity. Chemical analysis of spark‐decomposed SF₆ has identified and quantified the following compounds: SOF₂, SO₂F₂, SF₄, SOF₄, SiF₄, SO₂ and HF. Each of these gases, at concentration ranges expected in spark‐decomposed SF₆, were tested for cytotoxic activity toward hamster cells. Of the gases showing cytotoxic activity, SO₂F₂ and SOF₄ were similar in activity, as were SOF₂ and SF₄, while the behavior of SiF₄ was different from the rest. None of these individual gases, at concentrations expected in spark‐decomposed SF₆, has sufficient cytotoxic activity to account for the cytotoxic effect of spark‐decomposed SF₆ observed in our assay system. A four‐component mixture of some of the gases enumerated above (at concentrations overestimating their abundance in spark‐decomposed SF₆) was much less cytotoxic than the spark‐decomposed SF₆ gas. A mathematical simulation of the cytotoxic activity of a mixture of gases at concentrations found in spark‐decomposed SF₆ was made, assuming independent cytotoxic effects from each component. The simulated cytotoxic effect thus computed was less than that seen in spark‐decomposed SF₆. Since individual components or mixtures of the major decomposition products do not account for the observed biological activity of spark‐decomposed SF₆, this suggests there may be one or more components, present in the spark‐decomposed gas at very low concentrations, which may have a very strong cytotoxic activity.