Performance evaluation of a tailor-made passive sampler for monitoring of tropospheric ozone

Introduction

This study presents the performance evaluation of a tailor-made passive sampler developed for the monitoring of tropospheric ozone.

Methods

The performance of the passive sampler was tested in the field conditions in terms of accuracy, precision, blank values, detection limit, effects of some parameters such as sampling site characteristics and sampling period on the field blanks, self-consistency, experimental and theoretical uptake rates, shelf life and comparison with commercial passive samplers.

Results

There was an agreement (R ²?=?0.84) between the responses of passive sampler and the continuous automatic analyser. The accuracy of the sampler, expressed as percent relative error, was obtained lower than 15%. Method precision in terms of coefficient of variance for three simultaneously applied passive samplers was 12%. Sampler detection limit was 2.42???g?m^?3 for an exposure period of 1?week, and the sampler can be stored safely for a period of up to 8?weeks before exposure. Satisfactory self-consistency results showed that extended periods gave the same integrated response as a series of short-term samplers run side by side. The uptake rate of ozone was found to be 10.21?mL?min^?1 in a very good agreement with the theoretical uptake rate (10.32?mL?min^?1). The results of the comparison study conducted against a commercially available diffusion tube (Gradko diffusion tube) showed a good linear relationship (R ²?=?0.93) between two passive samplers.

Conclusions

The sampler seems suitable to be used in large-scale measurements of ozone where no data are available or the number of existing automated monitors is not sufficient.     

The impact of domestic wood burning on personal, indoor and outdoor levels of 1,3-butadiene, benzene, formaldehyde and acetaldehyde

The aim of this study was to quantify personal exposure and indoor levels of the suspected or known carcinogenic compounds 1,3-butadiene, benzene, formaldehyde and acetaldehyde in a small Swedish town where wood burning for space heating is common. Subjects (wood burners, n = 14), living in homes with daily use of wood-burning appliances were compared with referents (n = 10) living in the same residential area. Personal exposure and stationary measurements indoors and at an ambient site were performed with diffusive samplers for 24 h. In addition, 7 day measurements of 1,3-butadiene and benzene were performed inside and outside the homes. Wood burners had significantly higher median personal exposure to 1,3-butadiene (0.18 microg m(-3)) compared with referents (0.12 microg m(-3)), which was also reflected in the indoor levels. Significantly higher indoor levels of benzene were found in the wood-burning homes (3.0 microg m(-3)) compared with the reference homes (1.5 microg m(-3)). With regard to aldehydes, median levels obtained from personal and indoor measurements were similar although the four most extreme acetaldehyde levels were all found in wood burners. High correlations were found between personal and indoor levels for all substances (r(s) > 0.8). In a linear regression model, type of wood-burning appliance, burning time and number of wood replenishments were significant factors for indoor levels of 1,3-butadiene. Domestic wood burning seems to increase personal exposure to 1,3-butadiene as well as indoor levels of 1,3-butadiene and benzene and possibly also acetaldehyde. The cancer risk from these compounds at exposure to wood smoke is, however, estimated to be low in developed countries.     

Levels of chlorinated compounds (CPs, PCPPs, PCDEs, PCDFs and PCDDs) in soils at contaminated sawmill sites in Sweden

Soil samples from five contaminated sawmill sites in Sweden were characterized with respect to chlorophenols (CP), chlorinated phenoxy phenols (PCPP, hydroxylated chlorinated diphenyl ethers), chlorinated diphenyl ethers (PCDE), chlorinated dibenzofurans (PCDF) and chlorinated dibenzo-p-dioxins (PCDD). The composition of chlorinated compounds in the soil samples was compared to the composition of two preservatives commonly used in the Scandinavian wood impregnation industry: the 2,3,4,6-tetrachlorophenol preservative called Ky-5 and the pentachlorophenol preservative Dowicide G. The levels of CPs in the soil samples ranged from 0.1 to 4500 mgkg-1 d.w., PCPPs from <0.15 to 940 mgkg-1 d.w., PCDEs from <38 to 6800 microgkg-1 d.w., PCDFs from 7.4 to 18000 microgkg-1 d.w. and PCDDs from 9.9 to 35000 microgkg-1 d.w. The resulting WHO-TEQ of PCDD/Fs in the soil samples ranged from 0.14 to 3000 microgkg-1 d.w. Despite a wide range of concentrations the congener compositions were similar within tetrachlorophenate and pentachlorophenate contaminated soils respectively. The contamination at each sawmill site may be linked to the use of either a tetrachlorphenol preservative, e.g. Ky-5, or a pentachlorophenol preservative, e.g. Dowicide G. Best-fit calculations were used to compare the chlorinated phenol contents of the preservatives to those of the soil samples. This revealed a positive correlation between the hydrophobicity (logKow) of contaminants and the ratio of their levels in soil to preservatives. The relative abundance of the chlorinated compounds varied greatly between the five sites studied, suggesting that their transport parameters differ substantially.     

Do males and females differ in the feeding of large and small siblings? An experiment with the bluethroat

Males and females have been reported to differ in their feeding of large and small siblings in several species of birds. According to recent hypotheses, this phenomenon may be related to a sexual conflict over avian hatching patterns. We designed an experiment to test for the existence of such a sex difference by manipulating nestling size hierarchies of the bluethroat (Luscinia s. svecica) in two directions; half the broods were “asynchronized” to yield large size-differences within broods and the other half were “synchronized” to yield small size-differences. In all broods, nestlings were categorized as being either large or small according to body mass. We recorded male and female food distribution by video early (day 4 after hatching) and late (day 8) in the nestling period. Males and females did not differ in their distribution of food among different-sized nestlings. With large size-differences, both males and females fed large nestlings nearly twice as often as small ones. In contrast, when the size-differences were small, food was more evenly distributed among nestlings. Early in the nestling period, males fed more nestlings during each feeding visit than did females. Our finding that male and female bluethroats do not differ in the feeding of large and small siblings is in contrast to most previous studies. Variation in costs and benefits to males and females from feeding different-sized nestlings, and restrictions to parental choice due to nestling interactions, may explain interspecific variation. Received: 27 June 1997 / Accepted after revision: 26 January 1998     

Modeling the Effect of Liming on Calcium Concentration in Swedish Lakes

To abate the severe acidification of Swedish lakes are about 7% directly limed (AL-lakes). These are important to include when assessing acidification. Consequently, we need to estimate their chemical status as if they were not lime-affected. We hypothesize that there is a spatial dependence for calcium (Ca) and magnesium (Mg) concentrations. Spatial variation is determined using variograms. We study lakes within two 150 ∗ 150 km quadrates (EMEP150-grid) in the middle and southern parts of Sweden. We model Ca in AL-lakes using the Ca and Mg concentrations in nearby, unaffected lakes (UL-lakes). The mean Ca/Mg for the three or seven closest UL-lakes is used. We assume that Ca/Mg is constant for UL-lakes and that Mg unaltered by liming. For UL-lakes, Ca and Mg are spatially dependent. For AL-lakes, there is a spatial dependence for Mg, but, as anticipated, not for Ca. The modeled Ca for UL-lakes show a good correspondence with measured Ca; r ² > 0.6; slopes close to 1 and intercepts almost 0. Using three or seven nearby lakes when modeling Ca give similar results. Modeled Ca was higher than measured Ca for 36% (three closest lakes) and 38% (seven closest) of the modeled AL-lakes in the middle part of Sweden. The corresponding results for the southern part were 10% and 9%, respectively. This model is an acceptable estimator of Ca in limed lakes and for estimating critical loads and acidification status on an EMEP-scale.     

Herbivorous amphipods inhabit protective microhabitats within thalli of giant kelp <Emphasis Type="Italic">Macrocystis pyrifera</Emphasis>

Many small marine herbivores utilize specific algal hosts, but the ultimate factors that shape host selection are not well understood. For example, the use of particular microhabitats within algal hosts and the functional role of these microhabitats have received little attention, especially in large algae such as kelps. We studied microhabitat use of the herbivorous amphipod Peramphithoe femorata that inhabits nest-like domiciles on the blades of giant kelp Macrocystis pyrifera. The vertical position of nest-bearing blades along the stipe of the algal thallus and the position of the nests within the lateral blades of M. pyrifera were surveyed in two kelp forests in northern-central Chile. Additionally, we conducted laboratory and field experiments to unravel the mechanisms driving the observed distributions. Peramphithoe femorata nests were predominantly built on the distal blade tips in apical sections of the stipes. Within-blade and within-stipe feeding preferences of P. femorata did not explain the amphipod distribution. Amphipods did not consistently select distal over proximal blade sections in habitat choice experiments. Mortality of tethered amphipods without nests was higher at the seafloor than at the sea surface in the field. Nests mitigated mortality of tethered amphipods, especially at the seafloor. Thus, protective microhabitats within thalli of large kelp species can substantially enhance survival of small marine herbivores. Our results suggest that differential survival from predation might be more important than food preferences in determining the microhabitat distribution of these herbivores.     

Introduction of cob(I)alamin as an analytical tool: application to reaction-kinetic studies of oxiranes

The strongly nucleophilic cob(I)alamin, i.e. Vitamin B₁₂ with Co(III) reduced to Co(I), is introduced as a trapping agent in the determination of concentrations of electrophilic reagents. This compound was applied, in comparison with the previously used moderately reactive nicotinamide (H.J.C.F. Nelis and J.E. Sinsheimer (1981). Anal. Biochem., 115, 151.). Oxiranes, metabolites of 1-alkenes, were chosen as model electrophiles. The reagents (nicotinamide and cob(I)alamin) were evaluated in the determination of the rates of reaction toward valine methylamide, a model of N-terminal valines in hemoglobin often used for monitoring of doses in vivo of genotoxic carcinogens. The rate constants for reaction at 37°C with valine methylamide (k _VMA) determined by the cob(I)alamin and nicotinamide procedure, respectively, were for ethylene oxide (1.6, 1.7), propylene oxide (0.9, 1.1), 1,2-epoxybutane (0.7, 0.8) and 1,2-epoxyoctane (0.5, 0.6) M^?1?h^?1, decreasing with increasing number of carbons of the oxirane. Concentrations of oxiranes trapped with nicotinamide are underrated in reaction mixtures containing valine methylamide due to consumption by reaction with the competing nucleophile, a disturbance that is not observed in trapping with cob(I)alamin which reacts about 10⁵ times faster than nicotinamide. Cob(I)alamin which was demonstrated to be an efficient nucleophile for trapping of electrophiles, also in the presence of competing nucleophiles, is promising as an analytical tool in toxicological studies of reactive compounds. Furthermore, cob(I)alamin can be used to detect, measure and compare electrophilic reactivity of chemical substances, a property that is associated with genotoxic potency.     

Benefits of extra-pair mating may depend on environmental conditions—an experimental study in the blue tit (Cyanistes caeruleus)

Extra-pair mating constitutes a relatively common reproductive strategy in many socially monogamous bird species. This strategy may considerably improve reproductive success of males, but female benefits from extra-pair matings still remain unclear and empirical evidence is scarce. This may be because genetic benefits of extra-pair mating are not always revealed. It is possible that they are shown only in unfavourable environmental conditions and hence problems arise with detecting differences between within- and extra-pair offspring whose performance is measured under favourable conditions. In order to test this prediction, we manipulated environmental conditions by altering brood sizes of blue tits and compared phenotypic characteristics of within- and extra-pair offspring in mixed-paternity broods. We found that extra-pair young exhibited a higher response to phytohemagglutinin in comparison to within-pair young, but this was only observed among nestlings from experimentally enlarged broods. These results indicate that genetic benefits may interact with the environment, and thus benefits of extra-pair mating are likely to become visible only when conditions are relatively unfavourable.