Persistent organochlorines in beluga whales (Delphinapterus leucas) from the St Lawrence River estuary--I. Concentrations and patterns of specific PCBs, chlorinated pesticides and polychlorinated dibenzo-p-dioxins and dibenzofurans

Blubber samples from beluga whales (Delphinapterus leucas) in the St Lawrence River estuary were analysed for PCB congeners (ortho- and non-ortho-substituted) and other persistent organochlorines as well as chlorinated dibenzo-dioxins/furans (PCDD/Fs). Major individual components (mean concentrations > 1 microg g(-1)) were 4,4'-DDE, -DDD and -DDT, T12 (a toxaphene-related compound), trans-nonachlor, oxychlordane, mirex, HCB, tris(p-chlorophenyl) methane and dieldrin. Concentrations of SigmaPCBs (8.3-412 microg g(-1)), SigmaDDT (3.36-389 microg g(-1)) and mirex (0.18-6.8 microg g(-1)) were particularly elevated relative to other odontocetes in Canadian waters. SigmaDDT, PCBs (as Aroclor), mirex and T12 concentrations were positively correlated with age of adult females (> 10 years) but only weakly, or not significantly, correlated with age of adult males. PCDD/Fs were present at low ng kg(-1) levels and consisted mainly of penta- and hexachlorofurans, and hepta- and octachlorodioxin. CB126 (3,3',4,4',5-PCB) was the most prominent non-ortho-substituted PCB congener in beluga blubber. Total TCDD toxic equivalents averaged 330 ng kg(-1) in females and 1400 ng kg(-1) in males and were dominated by CB126, and the mono-ortho-substituted congeners CB105 and CB118. Biomagnification factors (BMFs) for mirex and SigmaPCB from fish to beluga ranged from 11 to 16, and were similar to BMFs in Arctic animals, indicating that elevated levels in St Lawrence animals are a consequence of relatively high levels of recalcitrant organochlorines in prey of the beluga in the St Lawrence river system.     

Examination of environmental quality of raw and composting de-inking paper sludge

Paper sludges were traditionally landfilled or burned. Over the years, the use of paper sludges on soils has increased, as well as the concerns about their environmental effects. Therefore, the chemical characterization of paper sludges and their young (immature) compost needed to be investigated, and over 150 inorganic and organic chemicals were analyzed in de-inking paper sludge (DPS). In general, nitrogen, phosphorus and potassium contents were low but variable in raw DPS and its young compost. The contents of arsenic, boron, cadmium, cobalt, chromium, manganese, mercury, molybdenum, nickel, lead, selenium, and zinc were also low and showed low variability. However, the copper contents were above the Canadian compost regulation for unrestricted use and required a follow-up. The fatty- and resin acids, and polycyclic aromatic hydrocarbons were the organic chemicals measured at the highest concentrations. For resinic acids, care should be taken to avoid that leachates reach aquatic life. For polycyclic aromatic hydrocarbons, naphthalene should be followed until soil content reaches 0.1 microg g(-1), the maximum allowed for soil use for agricultural purposes according to Canadian Environmental Quality Guidelines. In young compost, the concentration of these chemical families decreased over time and most compounds were below the detection limits after 24 weeks of composting. In raw DPS, among the phenol, halogenated and monoaromatic hydrocarbons, dioxin and furan, and polychlorinated biphenyl families, most compounds were below the detection limits. The raw DPS and its young compost do not represent a major threat for the environment but can require an environmental follow-up.     

Chemical fingerprinting applied to the evaluation of marine oil pollution in the coasts of Canary Islands (Spain)

Chemical fingerprinting approach to environmental assessment is illustrated in the evaluation of marine oil pollution in the coasts using two limpet species as bioindicator organisms, and based on profiles and concentrations of n-alkanes and aromatic hydrocarbons in their tissues. Accidental and chronic releases of hydrocarbons can contaminate the marine environment of the Canary Islands not only because of their geographical situation but also because of the very dense tanker traffic around. This situation affects coastal areas, fishing activities, tourism resort, etc. Concentrations of n-alkanes and aromatic hydrocarbons (polycyclic aromatic hydrocarbons and methyl-polycyclic aromatic hydrocarbons) in the soft tissues of the marine intertidal and subtidal limpets, Patella crenata and Patella ullysiponensis aspera, were evaluated. Limpet samples were collected at monthly intervals, at three locations on the southeast coast of Tenerife over a 3-year period (1991-93). Levels of hydrocarbons found in limpets are similar to concentrations found in unpolluted areas around the world. From application of principal component analysis, the interpretation of variable loading plots gives information on variable correlation and can be used to distinguish among potential sources of pollution and the ability of studied molluscs to be used as bioindicator organisms.     

Effect of sulfur dioxide and sulfite on photochemical energy storage of isolated chloroplasts--a photoacoustic study

Photoacoustic spectroscopy was used to study the effect of sulfite and SO(2) on isolated corn mesophyll chloroplasts by monitoring the photochemical energy storage. Sulfite incubation of isolated chloroplasts, either in light or in darkness, caused a decrease in photochemical energy storage. The more pronounced decrease in light indicates a light-dependent sulfite inhibitory site(s) in chloroplasts. Also diphenylcarbazide caused a partial recovery of energy storage in sulfite treated chloroplasts indicating a possible site of damage at the water oxidizing system. Although the chloroplast membranes were found to be insensitive to high concentrations of SO(2) for relatively short exposure periods (10 min) in light, exposure of chloroplasts to 28.5 ng cm(-3) SO(2) for 10 min caused a decrease in energy storage. An attempt was made to explain the mechanism of action of sulfite and SO(2) in chloroplasts.     

Influence of pre-treatment step on PAHs analyses in contaminated soils

There is no specific standardization for the pre-treatment of a soil sample for PAHs analyses. The ISO/FDIS 14507 method for soil quality gives a guidance for sample pre-treatment before measurement of organic contaminants in soil. It refers to cryogenic crushing which is not so easy to carry out. So, analysts lead to develop in house methods which can be very different from a laboratory to another and can involve deviations in the pollution quantification. This study has explored different ways of drying, grinding and sieving in order to determine the influence of the soil sample handling on the measured pollutant concentration. It appears that the influence of pre-treatment depends on the soil nature and on the PAHs distribution. As a conclusion, it is advised "light" drying ways like air drying or drying at 40 degrees C in a drying oven instead of more "drastic" ways (freeze-drying, cryogenic crushing) which can induce some losses. Crushing and sieving are also recommended for more reproducible measures.     

Formation of PCDD/Fs in the sintering process: role of the grid-Cr2O3 catalyst in the de novo synthesis

The sintering process is among the major sources of the very toxic polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in the environment. At the industrial scale, it has been shown that dust collected on the grid, which supports the feed, contains PCDD/Fs amounts between the values found in the bottom of the cake and the values found on dust collected during gas sampling in the wind boxes. This fact suggests that the grid, containing 25wt.% of chromium, could have a catalytic activity in PCDD/Fs formation during the sintering process. This research tries to study this potential role. The de novo synthesis of PCDD/Fs is simulated at laboratory scale by thermal treatments of samples mixed with grid filings or Cr2O3. The thermal experiments performed with E.S.P. dust (dust collected in the electrostatic precipitator of a sintering plant) or graphite mixed with grid filings do not allow to confirm a role of the grid in PCDD/Fs formation during the industrial process. On the other hand, it has been shown that Cr2O3 can be considered as a catalyst in the de novo synthesis of PCDD/Fs. This compound takes place in the two steps of the de novo synthesis: the degradation of the carbon matrix as well as the chlorination reactions.     

Ozone exposure among Mexico City outdoor workers

In researching health effects of air pollution, pollutant levels from fixed-site monitors are commonly assigned to the subjects. However, these concentrations may not reflect the exposure these individuals actually experience. A previous study of ozone (O3) exposure and lung function among shoe-cleaners working in central Mexico City used fixed-site measurements from a monitoring station near the outdoor work sites as surrogates for personal exposure. The present study assesses the degree to which these estimates represented individual exposures. In 1996, personal O3 exposures of 39 shoe-cleaners working outdoors were measured using an active integrated personal sampler. Using mixed models, we assessed the relationship between measured personal O3 exposure and ambient O3 measurements from the fixed-site monitoring station. Ambient concentrations were approximately 50 parts per billion higher, on average, than personal exposures. The association between personal and ambient O3 was highly significant (mixed model slope p < 0.0001). The personal/ambient ratio was not constant, so use of the outdoor monitor would not be appropriate to rank O3 exposure and evaluate health effects between workers. However, the strong within-worker longitudinal association validates previous findings associating day-to-day changes in fixed-site O3 levels with adverse health effects among these shoe-cleaners and suggests fixed-site O3 monitors may adequately estimate exposure for other repeated-measure health studies of outdoor workers.     

Chloride imbalances in soil lysimeters

The assumption that soil neither acts as a source or a sink of chloride is evaluated by incubating soil cores in lysimeters in a climate chamber under controlled conditions. Some of the lysimeters acted as a sink while others acted as a source of chloride. Considerable amounts of organic chlorine were lost by leaching. The loss by leaching of organic chlorine could only explain part of the discrepancy in the lysimeters where the soil acted as a sink and it could certainly not explain the cases where the soil acted as a source.The storage of organic chlorine was four times larger than the storage of chloride and comparably small changes in the organic chlorine storage will thus have a considerable influence on the chloride budget. However, the soil was too heterogeneous to determine whether a change in the storage had taken place or not. It is concluded that the observed chloride surplus and also, at least to some extent, the observed chloride deficit, most likely was caused by net-changes in the storage of organic chlorine in soil. An inverse correlation was found between the initial chloride content of the soil and the imbalance in the chloride budget.Dry deposition of chloride is generally assumed to equal the run-off minus the wet deposition. Extrapolation to the field situation suggests that the output of organic chlorine by soil leachate is at risk to cause an underestimation of the dry deposition by about 25%.     

Phytoplankton and water quality characterization: experiences from the Swedish large lakes Mälaren, Hjälmaren, Vättern and Vänern

Phytoplankton and environmental variables have been monitored in the large Swedish lakes M?laren, Hj?lmaren, V?ttern and V?nern since the 1960s. Measures to reduce phosphorus input and industrial waste products were taken during the 1970s. The phosphorus loading was then reduced by 90-95% resulting in a halving of the phosphorus concentrations in the most affected basins. The phytoplankton community reacted rapidly with decreased biomasses of cyanobacteria in summer as well as decreased biomasses of spring diatoms and cryptophycean flagellates. Other reactions were a contracted period of water-bloom, an increased taxon richness, an increased evenness in the biomass over the growth season, and a change in the species size structure within the phytoplankton community. Furthermore, the species richness in the large lakes is compared in relation to lake characteristics. A presentation of the occurrence of toxic cyanobacteria in the lakes is also given. Maximum-minimum values of 13-0.1 micrograms microcystin L-1 are established in connection with water-blooms in Hj?lmaren and M?laren. The use of phytoplankton as a monitoring variable to detect water-quality changes is outlined and assessment criteria are presented.