From critical levels to critical loads for ozone: a discussion of a new experimental and modelling approach for establishing flux-response relationships for agricultural crops and native plant species

Present critical levels for ozone (O3) for protecting vegetation against adverse effects are based on exposure-response relationships mainly derived from open-top chamber experiments and are expressed as an Accumulated exposure Over a Threshold of 40 ppb (AOT40). In that context with a revision of the UN (United Nations)-ECE (Economic Commission for Europe) Gothenburg protocol, AOT40 values should be replaced by flux-oriented quantities, i.e. in the end by critical loads. At present, the database for the derivation of critical loads for O3 is extremely inadequate. Furthermore, the currently available flux-response relationships are also derived from open-top chamber experiments. The use of a relationship for spring wheat in a risk assessment for an agricultural site in Hesse, Germany, demonstrates in principle, the applicability of the critical load concept for O3. Comparisons of diurnal variation of stomatal uptake and AOT40 showed that a major part of toxicologically effective stomatal uptake occurred before noon whereas the AOT40 values were dominated by the O3 concentrations during afternoon. In other words, the AOT40 exposure index do not adequately address the O3 burden during hours when plants are sensitive to O3 uptake. However, due to the differences in radiation, air temperature and humidity between the chamber and the ambient microclimates, a derivation of flux-response relationships from chamber experiments is likely to be questionable, especially for species rich ecosystems: Here, without any changes in the pollution climate, significant modifications of species composition as well as an earlier beginning of the growing season has been previously observed. To overcome the problems associated with chamber-derived flux-response relationships, a new experimental and modelling concept, was developed. The approach, briefly described in this paper, combines methods in air pollution toxicology and micrometeorology. As an analogy to the free-air fumigation concept, O3 is released into the air by an injection system above the plant canopy. The assessment of dispersion and surface deposition of O3 released is based on Lagrangian trajectory modelling. Depending on wind direction and velocity, atmospheric stratification and surface roughness, without any disturbance of the microclimate and micrometeorology, several sub-areas can be identified around the source position with differing deposition rates above the ambient level. Taking into account the actual O3 background deposition, deposition rates and vegetation responses observed in these sub-areas can easily be used to derive flux-effect relationships under ambient conditions and more realistic limiting values to protect our environment.     

Effects of elevated ozone on leaf delta13C and leaf conductance of plant species grown in semi-natural grassland with or without irrigation

Stable carbon isotope ratios (delta(13)C) and leaf conductance (g(s)) were measured (2002, 2003) in Holcus lanatus L., Plantago lanceolata L. Ranunculus friesianus (Jord.), and Trifolium pratense L. at two levels of ozone (O(3)) with or without irrigation. In non-irrigated control plots, R. friesianus showed the least negative delta(13)C, and the smallest response to the treatments. Irrigation caused more negative delta(13)C, especially in H. lanatus. Irrespective of irrigation, O(3) increased delta(13)C in relationship to a decrease in g(s) in P. lanceolata and T. pratense. The strongest effect of O(3) on delta(13)C occurred in the absence of irrigation, suggesting that under field conditions lack of moisture in the top soil does not always lead to protection from O(3) uptake. It is concluded that in species such as T. pratense plants can maintain stomatal O(3) uptake during dry periods when roots can reach deeper soil layers where water is not limiting.     

Determination of some aliphatic and polycyclic aromatic hydrocarbons in marine sediments of the Baltic Sea

Two representative samples of surficial marine sediments have been studied, one from the northern Baltic Proper and the other from the Gulf of Finland. Aliphatic hydrocarbons were determined by gas chromatography on a fused silica capillary column, and six polyaromatic hydrocarbons were determined by gas chromatography-mass fragmentography. Hydrocarbons were extracted with a benzene-methanol mixture and ultrasonic agitation. The aliphatic hydrocarbons were tentatively identified by their retention times. The polyaromatic hydrocarbons (PAHs) were identified on the basis of their retention times and mass fragmentograms by direct comparison with those of standard compounds. The aliphatic hydrocarbon contents ranged from 0,1 to 2,6 μg/g dry matter. In both samples there was a clear maximum at n-C₁₇ and also a clear odd-carbon predominance. The PAH contents ranged from 4 to 120 ng/g dry matter. The PAH concentration was about 58 per cent higher in the sample from the Gulf of Finland than in the sample from the Baltic Proper.     

Recent trends of biocides in pikes of the Lake Päijänne

Pikes were sampled in May 1980 from three areas of the Lake Päijänne, Finland and analyzed for their contents of total mercury, methyl mercury, hexachlorobenzene (HCB), DDE, PCB and chlorophenolic residues. An improved method for methyl mercury determination was applied and 82–84 % methylation of mercury in pikes regardless of area or biological variation was observed. Statistical analysis with previous results from the same areas gave a very significant decreasing trend of mercury levels at all three areas from 1970 to 1980. Future levels of mercury in fish to be consumed as food could be estimated from the trend regression. The very low levels of DDE and PCB showed some increasing trend when the influence of fat contents was eliminated by covariance analysis. General appearance of HCB at sub-ppb level was observed. Also pentachlorophenol occured at 10–70 ppb (fresh weight) levels at all areas, but the other chlorophenols were abundant only at Tiirinselkä which is most contaminated by pulp bleaching effluents.     

The Biological System of the Elements (BSE)--a brief introduction into historical and applied aspects with special reference on "ecotoxicological identity cards" for different element species (e.g. As and Sn)

There are different methods to estimate and predict effects of chemical elements and corresponding speciation forms in biochemistry and toxicology, including statements on essentiality and antagonisms. Two approaches are given here: (1) "identity cards" describing biologically fundamental aspects of element chemistry and (2) qualitative discussions which assume the existence of (indirect ways into) chemical autocatalysis to be essential for maintaining life and permitting reproduction. The latter method, developed by the present authors, draws upon Stoichiometric Network Analysis, a safe procedure for complexity reduction in feedback networks) and provides estimates of concentration regimes for different elements suitable for survival and reproduction. The biochemical hierarchy level considered here is that of (metallo-)proteins. Thermodynamic toxicity aspects are given in correlations with DMSO solvent affinities and thiocyanate bonding modes. Effects of antagonists and of ion substitution within metalloenzymes or of metabolic simplification can be dealt with, likewise increased sensitivities within symbiotic relationships and within carcinomas are explained which are relevant for environmental monitoring and tumour therapy, respectively.     

Analysis of moisture findings in the interior spaces of Finnish housing stock

A grading system was developed to rate the moisture damage profile of dwellings and to study the relationship between moisture-induced indoor air problems and occupant health. A total of 630 randomly selected houses and apartments, built between 1950 and 1989, were visually inspected. Moisture observations were standardized into three damage levels. Thus, a system to classify the homes into three grades was devised. The two grades of homes associated with the highest levels of damage were graded as index homes. Overall, 51% of the sample had some kind of moisture fault in them and one in every three homes (33%) was classified as an index home. The mean number of damage incidents in the index dwellings varied from 1.4 to 2.6. The mean number of damage incidents in the reference homes was 0.28. Prevalence of index dwellings was significantly higher (p < 0.01) in houses (38%) than in apartments (26%). There was no major difference in the prevalence of index buildings in houses built in any particular decade (30-35%). Moisture was observed in 28% of bathrooms, in 10% of kitchens, and in 17% of other spaces. Indoor relative humidity (RH) levels were low in most homes.     

Organochlorine concentrations in diseased vs. healthy gull chicks from the northern Baltic

The population decline of the nominate lesser black-backed gull Larus fuscus fuscus in the Gulf of Finland (northern Baltic) is caused by an exceedingly high chick mortality due to diseases. The chick diseases include degeneration in various internal organs (primarily liver), inflammations (mainly intestinal), and sepsis, the final cause of death. The hypothesis of starvation causing intestinal inflammations (leading to sepsis) was tested by attempting to reproduce lesions in apparently healthy herring gull L. argentatus chicks in captivity. The herring gull chicks were provided a similar low food-intake frequency as observed for the diseased chicks in the wild. However, empty alimentary tract per se did not induce the intestinal inflammations and therefore, inflammations seem to be innate or caused by other environmental factors in the diseased lesser black-backed chicks. They had very high concentrations of PCB in their liver; but the concentrations were not significantly higher than those of the healthy herring gull chicks, indicating a common exposure area for both species (i.e. the Baltic Sea). When compared to NOEL and LOEL values for TEQs in bird eggs our TEQ levels clearly exceed most or all of the values associated with effects. Compared with published data on fish-eating waterbirds, the DDE concentrations in the diseased lesser black-backed chicks were well above the levels previously correlated with decreased reproduction, while the residues in apparently healthy herring gulls were below those levels. The DDE/PCB ratio in lesser black-backs was significantly elevated, indicating an increased exposure to DDTs as compared with most other Baltic and circumpolar seabirds. The possible exposure areas of DDT in relation to differential migration habits of the two gull species are discussed.     

Dissolved organic matter in pore water of freshwater sediments: effects of separation procedure on quantity, quality and functionality

Pore water was separated either with or without water extraction prior to centrifugation (7600 or 20 000 × g) in order to investigate the effects of separation procedure on the amount and properties of dissolved organic matter (DOM i.e. the material passing through a 0.45-μm filter) in three freshwater sediments. On the basis of solubility in alkaline, organic matter was concluded to compose of humic substances in two (S1 and S3) and of humin (S2) in one of the sediments. DOM in the samples was quantified by total organic carbon measurement. Specific UV-absorption (SUVA) and high performance size exclusion chromatography (HPSEC) analyses were used to characterize DOM. Sorption of pyrene was used as a measure for functionality of DOM. Both water extraction and centrifugation speed were shown to affect the properties of DOM; however, the effects were sediment dependent. Water extraction increased the amount of DOM separated from the two sediments that had humic character (S1 and S3). In most cases water extraction increased SUVA and shifted the molecular size distribution of DOM towards larger sizes. The separation procedure had also an effect on the functionality of DOM. In water extracted samples of S2 and S3 the sorption of pyrene was higher than in the corresponding samples separated without water extraction, whereas in S1 similar effect was not found. Generally, centrifugation speed had smaller effects on the properties of DOM than water extraction. The fact that the effects of separation procedure on DOM depend on the sediment characteristics complicates the comparison between samples and evaluation of functionality in field conditions.     

Polybrominated diphenyl ethers and traditional organochlorine pollutants in fulmars (Fulmarus glacialis) from the Faroe Islands

The observed high-level burdens of organohalogens among the residents of the Faroe Islands, needs to be explained. Long-finned pilot whale (Globicephala melas) blubber and meat are known sources of environmental exposure. The present study focus on the organohalogen contamination of the fulmar (Fulmarus glacialis). The compounds quantified in fulmar muscle, fat, and egg are PCBs, DDTs, hexachlorobenzene (HCB), and polybrominated diphenyl ethers (PBDEs). The dominating pollutants are the 4,4'-DDT metabolite 4,4'-DDE and the two PCB congeners, CB-153 and CB-180, which are present in geometric mean concentrations of 7100, 4700 and 2500 ng/g lipid weight (l.w.), respectively, in adult fulmar muscle. 4,4'-DDT and HCB concentrations are approximately 250 ng/gl.w., each. Concentrations in the eggs are about 50% of the fulmar muscle levels, due to differences in lipid amounts, 4% in muscle and 10% in the eggs, the exposure contribution on a fresh weight basis is almost the same. As a result, both the egg and the adult fulmar muscle may lead to a significant exposure risk, if consumed by humans. BDE-153, the most abundant PBDE congener in fulmar muscle, with a geometric mean concentration of 6.5 ng/gl.w., is much lower than the individual PCB congeners and 4,4'-DDE concentrations. In the adult fulmar muscle, the relative PBDE congener pattern is different from that previously observed in biota, with BDE-153 and BDE-154 as the dominating congeners, rather than BDE-47. In contrast, BDE-47 is the most abundant congener in juvenile muscle and subcutaneous fat. The summation operatorPBDE concentrations are almost the same in egg, muscle (adult and juvenile) and subcutaneous fat (juvenile). For the polybrominated biphenyl (BB-153) the concentrations are considerably higher in the adult bird and egg than in the juvenile bird; this is also seen for the PCB and 4,4'-DDE concentrations. PCB concentrations found in fulmar egg and muscle are in the same range as seen in the pilot whale, i.e. 590-5700 ng/gl.w. for CB-153. Hence humans are also exposed to PCBs at a reasonable degree via intake of fulmar and/or fulmar egg and not only via pilot whale blubber.