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.     

Statistical interpolation model for the description of ground pollution due to the TCDD produced in the 1976 chemical accident at seveso in the heavily contaminated zone “A”;

The influence of NTA on chromium genetic activity was studied in the D7 strain of Saccharomyces cerevisiae. At low dose (subgenotoxic) of sodium chromate (CrVI) (5mM), NTA increased the point mutation while at higher dose (25 mM) of chromate in the presence of NTA a decrease of point reverse mutation was observed. Probably NTA affected either the uptake of Cr(VI) favouring the intracellular reduction to Cr(III), or the recombinational repair of DNA breaks induced by chromate oxiding activity.

An increase of point (reverse) mutation was obtained in the experiments with NTA and chromium chloride, suggesting the hypothesis that NTA might interact with Cr(III) forming NTA‐Cr(III) complexes able to permeate cellular membranes and bind to DNA. In addition NTA genetic inactivity was confirmed.     

Hydrolysis of a model surfactant as measured using ACYL coenzyme a synthetase

Hydrolysis of a model nonionic surfactant, [1‐¹⁴C]methyl palmitate, was compared between porcine esterase and lipase using a new hydrolase assay. The assay incorporates acyl coenzyme A (CoA) synthetase to convert the hydrolytic product of methyl palmitate, palmitic acid, to its acyl CoA derivative; palmitoyl CoA is separated from unreacted substrate for quantitation by a highly efficient extraction. The assay achieves quantitative separation between product and substrate due to the high water solubility of the acyl CoA derivative, eliminating the need for time‐consuming chromatographic separations. After 60 min under optimal conditions, only 20 U/mL porcine hepatic esterase hydrolyzed 93.6+0.9% of 20μM methyl palmitate, while 100U/mL porcine pancreatic lipase was required to hydrolyze only 82.3 ±0.7% of the same substrate. While both enzymes detoxified the surfactant, esterase was more efficient, possibly indicating preferential specificity for simple monoesters; generally selective for endogenous triacylglycerols, lipase may be less specific for surfactants. However, together both enzymes may enable mammals to hydrolyze ingested nonionic surfactants from oil spill dispersants, reducing their toxicity.     

Characterization of airborne particulate matter in thessaloniki,Greece

TSP samples, collected at two stations in the area of Thessaloniki during the period July 1987‐June 1988, were analysed for heavy metals (Fe, Pb, Zn, Cu, Mn, Cr, Co, Ni and V). Flame and flameless atomic absorption spectrophotometry was used for metal determinations. Metals determined were characterized with respect to their origin from natural or man‐made emission sources. Source identification was attempted by relation of metal concentrations to wind direction, and interelement correlations.

Results obtained showed that Pb, Zn and Cu are emitted from man‐made sources (traffic, domestic heating, industry), V, Ni and Co are derived partially from natural and man‐made sources, while Cr is mainly soil‐derived.     

Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

Sorption‐desorption kinetics of some organochlorine insecticides in silt‐water suspensions

Kinetic (batch) sorption and desorption experiments for some organochlorine insecticides in silt‐water suspensions are described. The effect of possible experimental artifacts on the results is examined. The influence of the silt/water ratio on the linear sorption coefficient and on the “nonextractable”; solute fraction is determined. The sorption process is described in terms of some kinetic models.     

Cleanup by solid‐phase extraction and HPLC of organochlorine insecticides and PCBS in various nonfatty and fatty samples

An accurate, simple and cheap extraction and cleanup procedure for capillary GC analysis of organo‐chlorine insecticides (OCs) in vegetables (cabbage and carrots) at the ng/g level, and for soil at the μg/g level is presented. The cleanup is carried out on solid‐phase extraction (SPE) cartridges, filled with 500 mg silica, 1 g of deactivated Florisil (10% w/w water), and 100 mg of anhydrous sodium sulphate. Recoveries >90% are obtained. The cleanup of OCs in fatty samples on an HPLC LiChrosorb Si 100 column is evaluated for subsequent capillary GC analysis. Fractionation of OCs and Aroclor 1254 and 1260 on an HPLC Nucleosil 100 column appears to be satisfactory.     

Rainwater composition as a function of the cloud type

The influence of the type of clouds that produce precipitation in the rainwater composition was analyzed. Logroño, a remote station in the North of Spain was chosen for the analyses. Results prove that the rainwater composition from Cumulonimbus is different to the composition of the rainwater from the other clouds. In addition, the source of NO₃ ^? and SO₄ ^2? is studied in the different types of clouds. It is shown that the source is the soil except Stratocumulus formed from Cumulus in which the source is the gas‐particle conversion.     

Human resilience and environmental degradation: The eco-cultural link in the Sahel

The relationship between human resilience and environmental degradation was studied in the Sahel. The strongest predictors of human resilience were rate of environmental degradation, avoidance, problem solving and locus of control. Compared to pastoralists, agriculturalists were more stressed and marginalized. Women in all groups scored higher on marginalization and stress than men.