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.     

Transport of butyltins at the water‐air interface and the adsorptive behavior of tributyltin in the surface microlayer

The transfer dynamics and enrichment phenomena of monobutyltin chloride(MBT), dibutyltin chloride(DBT) and tributyltin chloride(TBT) at the water‐surface microlayer (SM) interface were studied. The transport processes of the three compounds at the interface are very fast in the estuarine environment. The mass transfer coefficients are 1.54 m/h for MBT, 2.16 m/h for DBT, 1.56 m/h for TBT. The effect of various factors, including pH, salinity, suspended particulate and temperature, on the adsorptive behavior of TBT in the water's surface microlayer was also studied.     

Photolytic decomposition of uc‐54229, a Proinsecticide of the Carbamate group

Phototransformation of UC‐54229 (1) [2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl‐N‐(trimethylamino acetyl)‐N‐methyl carbamate chloride] was studied under UV and visible light conditions. Photoirradiation of 1 with UV‐light resulted in the formation of five degradation products which on the basis of their mass and ¹H Nmr spectral analysis were characterised as 2, 3, 4, 5 and 6. It was observed that under the influence of light, UC‐54229 was degraded to acetyl‐carbofuran which under similar conditions underwent further transformation to the actual toxicant carbofuran. The degradation products or impurities present in 100% water soluble powder formulation were identified as carbofuran phenol and triethylamine hydrochloride.     

The use of the embryo‐culture techniques in the research on the Teratogenic and Mutagenic properties of metals†

Actually, embryos can be cultured from the one‐cell stage up to the blastocyst stage, and their development can be easily monitored at any time: severe effects caused by toxic compounds are traduced by rapid embryonic death, less pronounced effects can be expressed by a lowered cleavage activity or by an arrest of the development from a particular stage. The system can be improved by transferring the embryos at the blastocyst stage in another more complete medium where they can “implant”; and form an inner cell mass with differentiated ectoderm and endoderm. Since last years, it has also become possible to culture postimplantation rodent embryos for short periods involving a number of particularly critical stages of organogenesis, such as the formation and closure of the anterior neuropore. Embryo‐culture also represents a useful system to study cytogenetic effects of chemicals which are often linked to lethal or teratogenic effects. These different possibilities are illustrated by examples of studies already performed with metals, and dealing with their teratogenic and/or cytogenetic effects on pre‐ and postimplantation rodents.     

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.     

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.     

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.     

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.     

Gas phase equilibria for dibenzo‐p‐dioxin,dibenzo‐p‐furan and biphenyl in the C‐H‐O system

The gas phase equilibrium calculation for the C‐H‐O system at atmospheric pressure and temperature from 773 to 1773 K at intervals of 250 K was performed to understand the generation and decomposition behavior of dibenzo‐p‐dioxin (DD), dibenzo‐p‐furan (DF) and biphenyl (BP) in relation to the existing oxygen potential. It is possible to categorize these results into three regions from the viewpoint of this potential: region (A), region (B) and region (C) are that of the higher, modest and lower oxygen potential, respectively. In region (A), the equilibrium amounts of DD, DF and BP are nearly zero. In region (B), they increase once and then decrease with rise in temperature. In the most characteristic region (C), they increase uniformly with rise in temperature.     

Planning for the monitoring of pollutants from non‐stationary combustion sources†

The most important constituents of traffic exhaust are carbon monoxide, nitrogen oxides, volatile organic compounds, polycyclic hydrocarbons and lead. Satisfactory analytical methods are available for measuring these compounds, but the required expenditure in their application to air pollution studies is quite different. Due to correlations between the concentrations of several exhaust components in road air conclusions regarding the expected level of some substances can be drawn by measurement of another emitted compound. But the selection of indicator compounds must be made under the aspect of the source‐specific relationship of emitted substances. The temporal and spatial distribution of air pollutants in street air is affected by traffic emissions more than by meteorological conditions. “Fingerprints”; of typical organic gaseous components of traffic exhaust also were found in residential areas.     

Pollution from polychlorodibenzo‐p‐dioxins and furans: The case of several foundry plants in the Lombardy region

In 1991 a co‐operation between Public Health Office (U.S.S.L.) n° 18 of Brescia and the Chemical Section Laboratories of U.S.S.L. n° 38 of Milan concerning the possible environmental impact of foundry industrial activities performing metallic scraps recovering, has been undertaken.

Soil and surfaces have been classified in conformity with the National Toxicological Consultative Commission (C.C.T.N.) recommendation dated 12/02/1988'; owing to the characteristics of the processed material, besides heavy metals, polychlorodibenzo‐p‐dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and polychlorobiphenyls (PCBs) have been looked for.

The particulate matter collected from the filters positioned over the arc furnaces in 14 foundry plants has been characterized and classified, according both to C.C.T.N.¹ and to the Interministerial Board regulation dated 27/07/1985 for the first application of the Republic President Decree Law (D.P.R.) n° 915/1982, concerning wastes classification, based, in this case, on these toxic chlorinated compounds concentrations. From the very beginning, high levels of PCDDs and PCDFs have been detected, corroborating the very few literature data from foundry plants². The results obtained on 14 different foundries allow us to draw already some information, acceptable from the point of view of the statistical validity, about the pollution produced by this industry.     

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.     

Project Tocoen. the fate of selected pollutants in the environment. Part XIX. the phytotoxicity of organic and inorganic pollutants‐cadmium. The effect of cadmium on the growth of germinating maize plants

The effect of increasing cadmium concentration (10, 100 and 1000 μmol dm^‐3) on the growth, leaf area, content of assimilation pigments, cadmium content and the regulatory ability of the tissue of maize plants was investigated.

The results obtained document, already after 6 days, a significant decrease of dry weight, reduction of leaf area, chlorophyll a and b as well as carotenoids in plants grown in the nutrient solution containing 1000 μmol dm ^‐3 of cadmium. A highly significant inhibition of growth, leaf area and assimilation pigments in plants growing in the nutrient solutions with 100 and 10 μmol dm^‐3 of cadmium was registered after 17 days of cultivation. In plants growing in the nutrient solution containing 100 μmol dm^‐3 of cadmium a demonstrable reduction of the content of assimilation pigments was registered after 11 days of culture.

With increasing cadmium concentration in the nutrient solution as well as in the plant tissue after 6 and 17 days of culture both the range of the regulatory zone and the extent of optimum pH increased into the acid region. The pH values of the isoelectric point decreased with increasing cadmium content in the solution.     

Cadmium in the terrestrial environment: Impact of long‐range atmospheric transport∗

Cadmium is supplied to Southern Norway in considerable amounts by atmospheric transport from other areas of Europe. This has caused a very marked increase of Cd levels in the natural environment in this area. Evidence of the main source areas is inferred from air concentration studies coupled to trajectory analysis. The extent of contamination is indicated from deposition studies and investigations of Cd in peat cores and surface soils, including soil profile distributions. The Cd content of vascular plants is substantially higher in Southern Norway than in areas farther north and further transfer in terrestrial food chains is occurring and may eventually lead to increased human exposure.     

Photochemistry of halogenated benzene derivatives. part xii.∗ effects of sodium nitrite on the environmental phototransformation of bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) herbicide in water: The photoincorporation of nitrite ions into bromoxynil

Photoreactions of the herbicide bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) (1) were extensively studied in water containing various concentrations of sodium nitrite with radiation of wavelengths around 313 nm. In the absence of NaNO₂, the quantum yields for the photodecomposition of the herbicide I amounted to 0.054±0.005, while such data was in the range of 0.047 ±0.005 to 0.023 ±0.003 in the presence of 0.5 to 25.0 × 10^‐3 m of the inorganic salt. These quantum yield data for the phototransformation of 1 without and with the presence of sodium nitrite followed the Stern‐Volmer equation. The rates of the photolytic destruction of bromoxynil (1) in water were slower in the presence than in the absence of NaNO₂. For example, the irradiation of the 7.8 x 10^‐6M aqueous solution of 1 in the presence of 10 mM sodium nitrite gave rise to the production of three main photoproducts, viz., 3‐bromo‐4‐hydroxy‐5‐nitrobenzonitrile (2), 4‐hydroxy‐3‐nitrobenzonitrile (3), and an “unidentified photoproduct”; 4. In the case of this photoreaction of compound 1, the percentages of maximum concentration of the photoproducts 2, 3, and 4 were achieved after 14, 44.5, and 60‐min photolyses of 1, respectively; the starting material 1 completely disappeared after 60‐min photolysis. The photoproducts 2 and 3 were identified through the interpretation of the GC‐MS data. Both thhe mass and FT‐IR spectra of the product 4 indicated the possible presence of a COOH group in 4.     

Interrelation of Cd‐lon concentrations and the growth and activities of microorganisms in two growth media†

Partitioning of native or anthropogenic heavy metals in solid and solution phases of soil is a result of network of several physico‐chemical reactions. The attainment of equilibrium between two phases is also regulated by biochemical processes. For practical purposes, the bioavailability of metal present in soil is predominantly regulated by the soil solution phase which is in dynamic equilibrium with the solid phase. The results of a model laboratory and greenhouse growth experiments have been used to investigate the effect of Cd‐ion concentrations (either in soil solution or in nutrient solution) on the growth and activities of microorganisms. The soil solution has been simulated by preparing a suspension of soil with 0.1 M NaNO₃ (1: 2.5) equilibrated for two hours. Important conclusions are as follows:

Increase in Cd‐ion concentration in soil solution or in nutrient solution induces corresponding adverse effect on the growth and activities of microorganisms. Thus, it seems that Cd‐ion concentration is a more sensitive indicator for assessing the effect of metal pollution upon the growth and activities of soil microorganisms in comparison to total Cd contents.

During active microbial growth phase, a large part of the organically bound Cd was released in the soil solution which is largely bioavailable. This process is termed as mobilisation. There was momentary increase of Cd‐ion concentration in soil solution which intoxicated the growing organisms. After this stage, the Cd ions from the solution phase were removed by the newly formed solid phase (nonviable biomass) and were transformed in non‐available form. This process is termed as immobilisation.

The consequences and importance of these results for practical agriculture and in deciding the limits or guidelines on the maximum tolerable metal load in soils are discussed.     

Comparison of sample digestion procedures for the determination of trace elements in antarctic krill by GF‐AAS

Two independent digestion procedures for Antarctic krill samples were compared. Dry ashing (DA) and microwave (MW) acid‐assisted digestion were tested for decomposing the samples to determine essential (Cu, Fe, Cr) and toxic elements (Cd, Pb) by graphite furnace‐atomic absorption spectrometry (GF‐AAS). A mixture of HNO₃ and H₂O₂ as digesting agent was used in the microwave procedure. For the dry ashing digestion, the organic matter was oxidated at 480°C in an open system. Both digestion methods were compared in terms of accuracy and applied to the analysis of a certified reference material: MURST‐ISS‐A2 (Antarctic krill).

The detection limits for the five elements analysed ranged from 3 to 150 ng g^‐1. Both digestion procedures are suitable for the decomposition of krill samples. However, dry ashing is not recommended to determine Pb and Cd because losses can occur.     

Recovery efficiency of the hydrofluorocarbon (HFC‐134a) by activated carbons of different physicochemical properties

The adsorption characteristics of 1,1,1,2‐tetrafluoroethane (HFC‐134a) on activated carbon were investigated to evaluate the recovery efficiency of HFC‐134a by six activated carbons (two granular activated carbons (GAC1 and GAC2), one high‐surface area activated carbon (HAC), and three activated carbon fibers (ACF10, ACF15, and ACF20)). HFC‐134a adsorption on the activated carbons increased with increase in the specific surface area and pore volume of the activated carbon. The differential heat of the HFC‐134a adsorption decreased with increase in the percentage of the micropore volume to the total pore volume. The adsorption model of HFC‐134a on the activated carbon could be based on the Langmuir model. The constant a of the Langmuir plot of HAC and ACF20 is smaller than GAC1 or GAC2 and ACF10 or ACF15, respectively. The constant W_s of HAC has the largest value. The constant a was correlated to the heat of adsorption. It is concluded that the largest amount of HFC‐134a was adsorbed on HAC, and the least amount of interaction occurred between HFC‐134a and the HAC. The amount of HFC‐134a adsorbed on the activated carbons over time was applied to the Sameshima equation. The adsorption rate constant of HFC‐134a on HAC was the largest. The HAC could be suitable for the recovery of HFC‐134a.     

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.