Influence of phytoplankton on complexing capacity of seawater†

Differential Pulse Anodic Stripping Voltammetry (DPASV) was employed to measure Apparent Copper Complexing Capacity (L_t) and Stability Constants (K_s) of related cupric complexes of cell exudates of the phytoplanktonic alga Dunaliella salina. Three natural seawater samples collected 0.1, 2, 5 miles off the Tyrrhenian coast were used as culture medium. The measurements were carried out 1h and 7 days after the inoculum. Furthermore, on one culture the medium was passed through C₁₈‐SEP‐PAK cartridges in order to separate the cell exudates. The results show that Dunaliella salina influences the value of L_t but does not affect the value of K_s . The C₁₈SEP‐PAK retain only 50% of the ligands produced by the cells and capable of complexing copper.     

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.     

Polarographic investigations on the complexation of cadmium and zinc by thiol peptides

Complex formation of Cd²⁺ and Zn²⁺ with thiol derivatives has been investigated by differential pulse polarography. The binding of Cd²⁺ and Zn²⁺ with cysteine (CySH), glutathione (GSH) and the model peptide N‐acetyl‐cysteine‐methylamide (ASH) reveals different stoichiometry. Thus, Cd²⁺ forms 1:1 and 1:2 complexes with CySH while 1:2 and 1:4 complexes have been observed with GSH and ASH, respectively. Overall formation constants of Cd²⁺ with CySH (Iogβ ₂ 15.3) and with GSH (Iogβ5₂ 14.4) have been estimated using competitive complexation with nitrilotriacetic acid (NTA). Investigation of competition between Zn²⁺ and Cd²⁺ for the thiol complexation has underlined the role played by the amino group in CySH for the stabilization of Zn complexes in contrary to Cd complexes.     

Large plasmids governing multiple resistances to heavy metals: A genetic approach∗

Gram negative bacteria classified as Alcaligenes eutrophus and carrying large resistance plasmids (generally two) were found in various industrial sites highly contaminated by heavy metals (Zn⁺⁺, Cu⁺⁺, Co⁺⁺,...). These strains were detected by DNA hybridization with a probe made with a 9kb fragment (ccz⁺ fragment) encoding for resistances to Cd⁺⁺, Co⁺⁺ and Zn⁺⁺, and cloned from plasmid pMOL30. This plasmid was isolated from the representative strain A. eutrophus CH34 which harbours the plasmids pMOL30 (240 kb) and pMOL28 (165 kb). Phenotypes related to pMOL28 and pMOL30 include the tolerance to Cd⁺⁺, Co⁺⁺, Cr0₄ ⁼, Cu⁺⁺, Hg⁺⁺, Ni⁺⁺, Pb⁺⁺ and Zn⁺⁺. The described genetic properties of these plasmids refer to some cloned or mapped functions and to some plasmid rearrangements. Plasmid pMOL85 (250 kb) which is related to pMOL30 was also described. Its host (A. eutrophus DS185) was isolated from a zinc desert. pMOL85 can efficiently self transfer in plasmidfree derivatives.     

Singlet molecular oxygen—mediated photooxidation of monochloro and mononitrophenols. A kinetic study

A kinetic and mechanistic study on the aerobic dye sensitized photooxidation of the mono—nitro and chlorophenols was carried out. A singlet molecular oxygen mechanism operates in the photooxidation. Solvent and substituent effects, suggest the intermediacy of a complex with partial charge transfer character, as has been postulated for other phenols.

Chemical (reactive) and physical interactions of the substrates with singlet molecular oxygen were discriminated. Quantum yields for photooxidation (higher for the chlorophenols) range from 3 × 10^‐2 to 2 × 10^‐3, as measured by substrate or oxygen consumption. These values indicate the viability of a singlet molecular oxygen photooxidation as a way for the degradation of nitro and chlorophenol environmental contaminants.     

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.     

Fate of organo‐heavy metal complexes of sludges from domestic wastes in soils: A simplified modelization

Simplified models provided information on the binding ability of organic acids with trace elements, the distribution of the formed organo‐heavy metal complexes at different pH, and the biological stability (biodegradation ability) of these complexes.     

Dissipation and effect of chlorophenoxy herbicide on plant pigments and carbohydrates of sunflower (Helianthus annuus L.)

The dissipation pattern of the chlorophenoxy herbicides (2,4‐D and 2,4,5‐T) residues in sunflower plants (Helianthus annuus L.) has been studied along with its effect on the changes of plant pigments (chlorophyll‐a,b, total chlorophyll, carotene and anthocyanin), sugar and starch in different parts of the plant. The residues of 2,4‐D and 2,4,5‐T remained for larger period of time (10 days) at higher concentrations than the lower concentration. The concentrations of chlorophylls and carotene were found to be reduced with the application of both 2,4‐D and 2,4,5‐T. But the chlorophyll concentrations were slowly normalized accompanied with the reduction of the herbicide residues. For anthocyanin, there was no significant effect. In case of carbohydrate, the sugar concentration was found to be raised by all doses in leaf and stem. The change in starch content in different plant parts did not follow an uniform pattern at different doses of herbicides.     

Characterization of airborne particulate matter in Thessaloniki,Greece

A receptor modeling approach has been applied to identify and apportion sources of airborne particulate matter in Thessaloniki, Greece. The absolute principal component analysis source apportionment technique used, provided quantitative information regarding both source particle characteristics and impacts. The analysis identified four major sources of heavy metals within total suspended particles (TSP) in the centre of the city: oil burning, pyrometallurgical non‐ferrous metal processes, motor vehicles and soil resuspension. Their contributions to TSP estimated by regression on absolute principal component scores (APCS) were 12%, 8%, 5% and 4%, respectively. A similar analysis conducted for a sampling site close to the industrial area identified five major sources: oil burning, industrial Cr source, soil resuspension, pyrometallurgical non‐ferrous metal processes and motor vehicles with contributions 20%, 15%, 9%, 8% and 4%, respectively.