Biological dehalogenation and halogenation reactions

A large number of halogenated compounds is produced by chemical synthesis. Some of these compounds are very toxic and cause enormous problems to human health and to the environment. Investigations on the degradation of halocompounds by microorganisms have led to the detection of various dehalogenating enzymes catalyzing the removal of halogen atoms under aerobic and anaerobic conditions involving different mechanisms. On the other hand, more than 3500 halocompounds are known to be produced biologically, some of them in great amounts. Until 1997, only haloperoxidases were thought to be responsible for incorporation of halogen atoms into organic compounds. However, recent investigations into the biosynthesis of halogenated metabolites by bacteria have shown that a novel type of halogenating enzymes, FADH(2)-dependent halogenases, are involved in biosyntheses of halogenated metabolites. In every gene cluster coding for the biosynthesis of a halogenated metabolite, isolated so far, one or several genes for FADH(2)-dependent halogenases have been identified.     

Temporal and spatial relationships in fine particle strong acidity, sulphate, PM1O, and PM2.5 across multiple canadian locations

The Canadian Acid Aerosol Measurement Program (CAAMP) was established in 1992 to gain a better understanding of the atmospheric behaviour of fine particle strong acidity (“acid aerosols”) and to facilitate an assessment of the potential health risks associated with acid aerosols and particles in general. During 1992. 1993 and 1994, annular denuder and filter measurements were taken at four sites in Ontario, two in Quebec, three in the Atlantic Provinces and one in the greater Vancouver area. Mean fine particle sulphate concentrations (SO₄²⁻) were highest in southern Ontario (annual average ranged from 40–70 nmol m⁻³), lowest at a site in the Vancouver area (average = 16 nmol m⁻³) and second lowest in rural Nova Scotia. However, mean fine particle strong acid concentrations (H⁺) were geographically different. The highest mean concentrations were at the east coast sites (annual average of up to 30 nmol m⁻³). Acidities were lower in areas where the fine particle acidity experienced greater neutralization from reaction with ammonia. This included the major urban centres (i.e. Toronto and Montréal) and areas with greater amounts of agricultural activity, as in rural southern Ontario. On average, ambient concentrations of fine and coarse particle mass were larger in the urban areas and also in areas where SO₄²⁻ levels were higher. All the particle components were episodic. However, compared to SO₄²⁻ and fine particles (PM_2.5 or PM_2.1, depending upon inlet design), episodes of H⁺ tended to be less frequent and of shorter duration, particularly in Ontario. Saint John, New Brunswick, had the highest mean annual H⁺ concentration, which was 30 nmol m⁻³. H⁺ episodes (24 h concentration > 100 nmol m⁻³) were also the most frequent at this location. The high levels in Saint John were partially due to local sulphur dioxide sources and heterogeneous chemistry occurring in fog, which, on average, led to a 50% enhancement in sulphate, relative to upwind conditions.There was a substantial amount of intersite correlation in the day to day variations in H⁺, SO₄²⁻ , PM_2.5 and PM₁₀ (fine + coarse particles) concentrations, which is due to the influence of synoptic-scale meteorology and the relatively long atmospheric lifetime of fine particles. Sulphate was the most regionally homogenous species. Pearson correlation coefficients comparing SO₄²⁻ between sites ranged from 0.6 to 0.9, depending on site separation and lag time. In many cases, particle episodes were observed to move across the entire eastern portion of Canada with about a two-day lag between the SO₄²⁻ levels in southern Ontario and in southern Nova Scotia.     

Hydrophobicity of complex organic mixtures

Hydrophobicity is an important property in risk assessment of chemicals. A group parameter that reflects the hydrophobicity of technical mixtures is not yet available. However, many substances are complex organic mixtures, for which it is practically impossible to determine each component separately. An experimental procedure to measure the hydrophobicity of organic mixtures without knowledge of the individual components was developed and tested for a mixture of benzene and twelve chlorobenzenes. This procedure is based on separation of the mixture into fractions of increasing hydrophobicity by reversed-phase HPLC, after which the total molar concentration in each fraction is determined by vapour pressure osmometry. The obtained information on hydrophobicity can be used for assessing bioaccumulation and sediment sorption after emission of the mixture to water has occurred.     

Influence of kinetic sorption and diffusion on pesticide movement through aggregated soils

Laboratory studies were carried out to investigate solute leaching at different times from application in relation to temperature and initial soil moisture. Aggregates of a heavy clay soil were treated with a non-interactive solute (bromide) and the herbicides chlorotoluron, isoproturon and triasulfuron. The soil was incubated at 90% field capacity and either 5 or 15 degrees C. The influence of application to initially dry and initially wet aggregates on the behaviour of isoproturon was also investigated. At intervals, samples were either leached in small columns, centrifuged to characterise the fraction of chemical available in pore water under natural moisture conditions or extracted with organic solvents to assess total residues in soil. Bromide concentrations in leachate and in pore water extracted by centrifugation were constant with time. In contrast, availability for leaching and concentration in pore water of the herbicides decreased with increasing time from application in soil incubated at 15 degrees C. The effect of residence time was much smaller at 5 than at 15 degrees C. At the higher temperature, pesticide concentrations in leachate and pore water declined faster than would be expected from degradation alone, probably due to slow diffusion of the pesticides into soil aggregates where they are less available for leaching and/or slow sorption-desorption. The faster decline in availability for leaching at 15 than at 5 degrees C was attributed to faster degradation of the readily available fraction. There was no significant influence of initial soil moisture on either the leaching behaviour of isoproturon or its availability in soil water.     

Comparison of the method of diffusive gels in thin films with conventional extraction techniques for evaluating zinc accumulation in plants and isopods

The measurement of diffusive gels in thin films (DGT) has recently been developed to assess metal bioavailability in soils. The DGT-method is based on diffusion in a porous matrix. To test the predictive capabilities of the method with regard to metal bioavailability, a study was set up with 28 soils having a variety of textures and amounts of zinc salts added. Correlation and regression analyses were performed to compare DGT-extracted zinc levels to zinc concentrations obtained by extraction with 0.01 M CaCl(2) and 0.43 M HNO(3), digestion with aqua regia and the zinc concentration in pore water. The amount of zinc extracted with CaCl(2) correlated well with DGT-extracted zinc levels in all soils spiked with different amounts of ZnCl(2). A similar correlation was not found for zinc concentrations in soil samples collected in the field. Experiments were performed to compare zinc content in organisms and in soils. The organisms tested were plants (grass, lettuce and lupine) and the hard bodied soil dwelling isopod Oniscus asellus. Good correlations were found between zinc accumulation in grass and lettuce and the C(E) (effective concentration) measured by a DGT-device, CaCl(2) extracted zinc and the zinc content in the pore water of all soils. The correlation with C(E) was not significant for lupine, neither for spiked soils, nor for field soils (p< or =0.001). Zinc levels in the isopods were not significantly related to any set of zinc measurements. From a synthesis of all results obtained it is concluded that the DGT-methodology does not have an additional value in predicting bioavailability of zinc in terrestrial ecosystems as compared to conventional extraction methods.     

Knowledge and utilization of edible mushrooms by local populations of the rain forest of south Cameroon

Indigenous knowledge of edible fungi and their utilization by local populations were investigated in southern Cameroon from 1996 to 1999. Some 100 participants from the major ethnic groups, comprising Bantu farmers and Bagyeli (Pygmy) hunter-gatherers, were interviewed. Mushroom usage by 30 families, (319 persons), was monitored daily for over a year. Mushroom knowledge among both groups was extensive. Over 50 vernacular names were provided by respondents. In Bantu households, women and children, and to some extent hunters, harvest mushrooms. In contrast, the whole Bagyeli household participates. Bantu harvest mushrooms preferentially in secondary forests while Bagyeli collect them predominantly in primary forests. Mushroom consumption is low for both groups, 1.1 and 1.4 kg of fresh mushrooms per person per year, respectively, a rate that is much lower than in central and eastern Africa. The apparent discrepancy between extensive mushroom knowledge and rather infrequent mushroom consumption probably relates to the social valuation of mushrooms.     

Assessment of the sustainability of technology by means of a thermodynamically based life cycle analysis

Life cycle analysis is one of the tools in the assessment of the sustainability of technological options. It takes into account all effects on the ecosystem and the population which may endanger the possibilities of current and future generations. However, the main bottleneck in current LCA methodologies is the balancing of different effects, being all quantified on different scales. In this work, a methodology is proposed, which allows one to quantify different effects of the production, consumption and disposal of goods, and services on a single scale. The basis of the methodology is the second law of thermodynamics. All production, consumption and disposal processes affecting the ecosystem and the population, are quantified in terms of loss of exergy. The exergy content of a material is the maximum amount of energy which can be transformed into work at given environmental conditions. Next to the elaboration of the methodology, the new approach is illustrated by examples of the production of synthetic organic polymers, inorganic building insulation materials and different waste gas treatment options.     

Distribution and dynamics of larval populations of Anopheles messeae and A. atroparvus in the delta of the rivers Rhine and Meuse,The Netherlands

The distribution and ecology of mosquitoes of the Anopheles maculipennis complex were studied in the delta of the rivers Rhine and Meuse in the southwest of The Netherlands. The study area was previously malarious, with A. atroparvus being the only vector. 125 potential aquatic habitats of A. maculipennis were sampled, of which 47 (37.6%) contained larvae of this species complex. Larval densities varied from 7.4-325.93 larvae m-2. There was no correlation between chlorinity (@1000) of the water and presence and/or density of larvae. The presence of A. maculipennis was not associated with one particular aquatic floristic habitat, although larvae were often found together with floating algae (Enteromorpha spp.). Larvae were not found in areas experiencing tidal flooding. A newly developed PCR method was used for identification of the mosquito sibling species. Of 150 larvae examined, only 4 were identified as A. atroparvus. All other larvae examined were A. messeae. Adult mosquitoes were identified as A. messeae and 30 wild-caught mosquitoes had fed on domestic animals. Because most anophelines found in 1999 were A. messeae, it is concluded that the study area has undergone a dramatic ecological change since the previous anopheline investigations in 1935, causing the near extinction of A. atroparvus. This species was the only malaria vector in The Netherlands and therefore it is not expected that malaria can return to its former endemic status in the coastal areas of The Netherlands.     

Dioxins and related compounds: Status and regulatory aspects

Several countries have put much effort in dioxin research programmes with the aim to assess the risks of dioxin exposure, to identify dioxin sources and to quantify their contribution to environmental emissions and human exposure. In this review, the accent has been put on: sources of dioxins and their contribution to the total dioxin emissions, sources of human exposure and their contribution to exposure and measures to reduce emission and exposure. The information from countries with existing dioxin regulations is reviewed and compared. Uncertainties which hamper comparability of data are indicated. Results of measures and expectations for the near future are presented.