Influence of CO<Subscript>2</Subscript> on the micro-structural properties of spider dragline silk: X-ray microdiffraction results

The mechanical properties of spider dragline fibres are altered by CO₂ exposure under anaesthetizing conditions during the spinning process. In order to relate these macroscopic changes to a microscopic model, the extrusion of dragline silk was studied by synchrotron radiation microdiffraction. A brief exposure of a female Nephila senigalensis spider to CO₂ results after an incubation time of less than 7 min in the extrusion of a thread (two fibres) swollen with water. The data are interpreted for a model of crystalline -sheet domains containing nanofibrils, which reinforce a network of protein chains. The protein network absorbs water, leaving the nanofibrils unaffected. A continuous flow of CO₂ results in a co-extrusion of a dragline thread and an isotropic silk fraction, which probably has a glycine-rich sequence. Long CO₂ exposure reduces the axial alignment of nanofibrils, presumably due to a partial destruction of the amorphous network.     

Occurrence of THMs and HAAs in experimental chlorinated waters of the Quebec City area (Canada)

Haloacetic acids (HAAs) and trihalomethanes (THMs) were generated in bench-scale chlorination experiments using treated waters (prior to final chlorination) of the three major drinking water utilities of the Quebec City area. The purpose was to investigate the formation and occurrence of these chlorination by-products (CBPs) on a seasonal basis. Data for HAAs, THMs and other physico-chemical parameters were produced through a six-month sampling program with variable conditions of water quality, water temperature, applied chlorine dose and reaction time. In waters from the three utilities, chloroform (THM specie), dichloroacetic and trichloroacetic acid (HAA species) were the most prevalent compounds due to the low concentrations of bromide in the utilities' raw waters. Significant differences in CBP occurrence were noted between the three utilities' chlorinated waters, mainly due to the type of disinfectant applied to raw water. The use of pre-ozonation, as opposed to pre-chlorination (or direct chlorination) in one of the utilities appears to be the major factor contributing to that utility's potential for compliance with current THM and future HAA standards. Seasonal variations in THMs and HAAs were mainly associated with variations in organic precursors and to changes in water temperature (two parameters which vary widely on a seasonal basis in surface waters of southern Quebec), with CBP occurrence at its highest in spring. Statistical correlations between HAAs and THMs were moderate and only temperature appeared to affect the preponderance of one CBP or the other. Finally, a regression analysis was carried out aimed at associating each CBP to water quality and the experimental parameters. Thanks to their predictive ability, multivariate models seem to be the tools with the best potential for decision-making purposes.     

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) distributions in the Bay of Marmara sea: Izmit Bay

In 1999, the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), the total PAH and polychlorinated biphenyls (PCBs) were measured in sea water, sediment and mussels collected along the coast of Izmit Bay, the most important bay of the Marmara Sea. The total-PAH concentrations, measured by Spectrofluorometry were in the range of 1.16-13.68 microg/l in sea water, in the range of 30.0 1670.0 microg/g dry weight in sediments and in the range from 5.67 to 14.81 microg/g wet weight in edible part of mussel. HPLC revealed Phenanthrene (three rings), chrysene (four rings) and benz[a]antracene (five rings) to be the dominant PAHs in sea water, while 16 different PAHs compounds were observed and measured in mussel samples. The most pollution occured at Dogu Kanali and Dil Deresi where were the main rivers containing wastes fall into the the Izmit Bay. Although the maximum mono-ortho PCB concentrations in sea water were measured in the Dil Deresi River (26.33 ng/l) and the Solventa? (22.19 ng/l) stations, maximum PCB concentrations in mussels were measured in the SEKA (28.11 microg/kg) and the Dil Deresi River (25.68 microg/kg). The dominant congeners of PCBs were from tetra to hexachlorobiphenyls. The toxicity equivalent values were very low in sea water and mussels.     

Toxicity of eight polycyclic aromatic compounds to red clover (Trifolium pratense), ryegrass (Lolium perenne), and mustard (Sinapsis alba)

The effect of eight polycyclic aromatic compounds (PACs) on the seed emergence and early life-stage growth of three terrestrial plants (Sinapsis alba, Trifolium pratense and Lolium perenne) were studied in a greenhouse, using a Danish agricultural soil with an organic carbon content of 1.6%. After three weeks of exposure, seed emergence and seedling weight (fresh weight and dry weight) were determined. Exposure concentrations were verified with chemical analysis. The substances tested were four polycyclic aromatic hydrocarbons (fluoranthene, pyrene, phenanthrene and fluorene), the N-, S-, and O-substituted analogues of fluorene (carbazole, dibenzothiophene and dibenzofuran, respectively), and the quinoline representative acridine. Seedling growth was a far more sensitive endpoint than seed emergence for all substances. Concentrations estimated to give a 20% reduction of seedling fresh weight (EC20-values) ranged from 36 to 290 mgkg(-1) for carbazole, 43 to 93 mgkg(-1) for dibenzofuran, 37 to 110 mgkg(-1) for dibenzothiophene, 140 to 650 mgkg(-1) for fluoranthene, 55 to 380 mgkg(-1) for fluorene, 37 to 300 mgkg(-1) for phenanthrene, and 49 to 1300 mgkg(-1) for pyrene. For acridine, no toxicity was observed within the concentration range tested (1-1000 mgkg(-1)). As illustrated by the EC20-values, there was a rather large difference in sensitivity between the species, and T. pratense was the most sensitive of the species tested.     

Toxicity evaluation of organic sediment extracts resolved by size exclusion chromatography using rainbow trout hepatocytes.

The (geno)toxicity of sediment dichloromethane extracts and fractions obtained by size exclusion chromatography were evaluated to investigate effects based on size fractionation. In this study, three sediments were selected according to their incremental contamination in PAHs and in PCBs: Hamilton harbour, Toronto bay and lake St. Clair sediments. Heavy metals, total sulfur and elemental sulfur (S8) were also determined in the (un)fractionated sediment extracts. The liver cells were exposed to concentrations of sediment extracts and fractionated samples for 24 h at 15 degrees C, afterwhich cell viability, cytochrome P4501A1 activity, available free Zn, DNA damage and oxidative stress were determined. The results showed that the sediment extracts contained high levels of sulfur most of which was found in the low molecular weight (LMW) region, i.e., the 2000-50 atomic mass unit (amu) fraction. Elemental sulfur (S8) accounted for 14-41% of extractable sulfur and were found to elute in the post-column volume (PCV) fraction despite its molecular weight of 256 amu. Heavy metals were found mainly in the HMW (i.e. the > 2000 amu) fraction and LMW fractions and very few or none were observed in the PCV fractions. In sediment extracts, sublethal effects were present principally by the HMW and LMW fractions suggesting that some chemicals were also associated with high molecular weight compounds of extractable organic matter. Less toxicity or effect was sometimes found in the extract indicating an antagonistic effect of the contaminants. We found that cell viability and genotoxicity evaluations could be performed on the unfractionated extracts while EROD, available Zn and oxidative stress measurements should be performed on the LMW fractions because of possible antagonist or shielding effects. Considering the cytotoxic responses, the best toxicity ranking in respect to contaminant levels in sediment extract was obtained with the LMW and PCV fractions which accounted for most of the toxic responses in the chromatographic fractions. Moreover, the shielding effect could be explained, in part, by the association of LMW contaminants to large macromolecules.