Effect of liquid inhibitors on PCDD/F formation. Prediction of particle-phase PCDD/F concentrations using PLS modelling with gas-phase chlorophenol concentrations as independent variables

Emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) from municipal waste incineration are currently a subject of considerable public concern because of their extreme toxicity. PCDD/F formation in incineration processes is being studied widely, but little work has been done on their inhibition. We studied the effect of two liquid inhibitors, sodium ammonium hydrogen phosphate (NAHF) and urea (H2NCONH2), on PCDD/F formation in the combustion of liquid fuel doped with copper and chlorine using a pilot-scale plant. The inhibitors were injected into the flue gas stream at a temperature of 725 degrees C, whereupon both the chlorophenol and PCDD/F concentrations decreased. Particle-phase PCDD/F concentrations in particular decreased by up to 90% with NAHF and 70% with urea, but gas phase reduction took place only with urea. The results suggest that the formation of PCDD/Fs is hindered in the particle phase at the early stages of the PCDD/F formation chain, probably even before precursors such as chlorophenols have been formed. As a consequence, particle-phase PCDD/F concentrations can be predicted by a PLS (partial least-squares) approach with the gas-phase chlorophenol concentrations as independent variables. The structure and partial charges of Cu(+)-urea complex were calculated by the HF/3-21G basis set.     

Digit ratios have poor indicator value in a wild bird population

Early androgen exposure is known to have long-lasting effects on phenotype, behaviour and even fitness, but difficulties in measuring the exposure hinders the study of its importance in evolutionary context. Digit ratios have been highlighted as a potential easy-to-measure indicator of early steroid exposure, as they have been suggested to reflect steroid, mainly testosterone levels during prenatal development. However, evidence for digit ratios reflecting early steroid levels is weak, as experimental studies, especially in wild populations, are scarce. We studied the association between maternally derived yolk androgens and digit ratios (2D:4D, 2D:3D and 3D:4D) using both correlative data and a rather high level of experimental elevation of yolk androgens in a passerine bird, the pied flycatcher (Ficedula hypoleuca). We also examined whether digit ratios have indicator value in an evolutionary context by studying correlations between digit ratios and reproductive traits, secondary sexual traits and exploratory behaviour. We did not find any association between digit ratios and yolk androgen level either in correlative or experimental data. Digit ratios were neither related to any of the reproductive and secondary sexual traits or exploratory behaviour measured. There was, however, a sex difference in 2D:3D and 3D:4D of adult birds (due to second and fourth digits being shorter in females), which was not apparent in fledglings or captivity-raised juveniles. This suggests that either the sex difference may develop as late as during the sexual maturation for breeding. These results indicate that, in this species, digit ratios are not reliable markers of maternally derived yolk androgen exposure and that they bear little relevance as correlates of the adaptive traits we measured.     

Effect of urea on fly ash PCDD/F concentrations in different particle sizes

The effect of urea as an inhibitor for reducing polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in flue gases was studied in a pilot scale plant, together with the effect on the particle size distribution of these compounds. Total PCDD/F concentrations decreased by a maximum of 74%, the decrease being greatest for the most highly (octa-) chlorinated isomers. The PCDD/F reduction affected all the particle size classes when an adequate amount of urea was used (1% of the fuel input), which indicates that inhibition, unlike formation, is independent of the fly ash particle size distribution.     

Prenatal diagnosis of the infantile type of neuronal ceroid lipofuscinosis by electron microscopic investigation of human chorionic villi

Chorionic villus biopsy specimens were studied electron microscopically in six pregnancies at risk of the infantile type of neuronal ceroid lipofuscinosis (INCL). The biopsy was performed in all cases in the first trimester of pregnancy (8–10 gestation weeks) by the transcervical route. In one case, the biopsy was repeated at 17 weeks by the transabdominal procedure. In two pregnancies, the endothelial cells and, to a lesser extent, the mesenchymal cells of the chorionic villi contained unit membrane-bound inclusions typical of INCL. In both cases, the pregnancy was terminated and in one of them identical inclusions were found in the brains and kidneys of the fetus at 20 weeks of gestational age. The children from the remaining four pregnancies are healthy and have shown no signs of the disease.     

Early prenatal detection of diastrophic dysplasia

Diastrophic dysplasia, an autosomal recessive disorder, results in severe short-limbed dwarfism, progressive spinal and joint problems, and secondary psychosocial disability. The results of treatments are unsatisfactory. Four pregnant mothers at risk for an affected fetus were studied with an ultrasound scanner at 16 and 19 weeks of gestation. Each mother had a previous child with diastrophic dysplasia. The biparietal distance and the length of the long bones of the extremities were normal in three fetuses, whereas in one fetus there was a 30 per cent shortening of all long bones. The biparietal distance corresponded with the gestational age in all fetuses. In one fetus, diastrophic dysplasia was confirmed by fetoscopy and fetal radiograph at 19 weeks of gestation after the parents had decided to terminate the pregnancy. The skeletal radiograph and autopsy findings of the fetus verified the diagnosis. All other mothers were followed with repeated ultrasound examinations, and they delivered healthy babies. The retrospective follow-up of the four previous pregnancies and of the present one with affected fetuses disclosed that two mothers had had vaginal bleeding, two lymphedema, one abdominal pains, and one mother had had polyhydramnios. These complications were, however, mild and transient, and they could not be regarded as specific for pregnancies with affected fetuses.     

Formation of aromatic chlorinated compounds catalyzed by copper and iron

This study shows the catalyzing effects of iron and copper on the formation of chlorinated compounds such as chlorobenzenes (ClBzs), chlorophenols (CIPhs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Both total concentrations and congener distributions have been studied. The parameters and conditions varied during the combustion tests were the complete and incomplete combustion and the metal and chlorine addition. The incomplete combustion promoted the formation of organic chlorinated compounds in flue gas particles. Highly chlorinated congeners of PCDD/F were dominant in the flue gas particles, whereas the importance of lower chlorinated congener were increased in the gas phase. In the complete combustion conditions the concentrations of PCDD/Fs increased when the degree of chlorination were high, nevertheless the concentrations of tetra and penta PCDD/Fs were higher in the gas phase than the concentrations in the fly ash particles. Organic chlorine promoted the formation of chlorinated compounds more effectively than inorganic chlorine, which instead promoted the formation of PCDD/Fs in the gas phase, especially with copper catalyst. Different concentration levels of chlorinated compounds were observed in the gas phase and in particles when the chlorine source and combustion conditions were varied from incomplete to optimum conditions. Both copper and iron seem to have a catalytic effect on PCDD/F formation.     

Lead poisoning and other human-related factors cause significant mortality in white-tailed eagles

The white-tailed eagle (Haliaeetus albicilla) suffered a severe population decline due to environmental pollutants in the Baltic Sea area ca. 50 years ago but has since been recovering. The main threats for the white-tailed eagle in Finland are now often related to human activities. We examined the human impact on the white-tailed eagle by determining mortality factors of 123 carcasses collected during 2000–2014. Routine necropsy with chemical analyses for lead and mercury were done on all carcasses. We found human-related factors accounting for 60% of the causes of death. The most important of these was lead poisoning (31% of all cases) followed by human-related accidents (e.g. electric power lines and traffic) (24%). The temporal and regional patterns of occurrence of lead poisonings suggested spent lead ammunition as the source. Lead shot was found in the gizzards of some lead-poisoned birds. Scavenging behaviour exposes the white-tailed eagle to lead from spent ammunition.     

A comparison of two cartographic exposure methods using Fucus vesiculosus as an indicator

Morphological variation and vertical distribution of Fucus vesiculosus were quantified at several sites in the Finnish archipelago (Baltic Sea). F. vesiculosus samples were obtained from skerries at geographical distances of 1 km or more (large scale) and at intervals of ca 100 m around a single island (small scale). The results were examined in relation to wave exposure, calculated by Baardseth and effective fetch cartographic methods. Despite the fact that the exposure indices were calculated differently they correlated strongly. Vegetative morphological characteristics of F. vesiculosus illustrate the morphological differences both within and between exposure gradients. The tallest and widest F. vesiculosus plants were found at the sheltered end of the large-scale exposure gradient. Those from equally sheltered sites of the island were smaller in all respects. Thus, the trend from small narrow plants to large wide sheltered plants was expressed differently over the different geographical scales. Consequently localities with similar exposure indices may have morphologically different F. vesiculosus populations. Shores with similar cartographic exposure indices can be different in nature. Underwater topography and shore locations, either close to the mainland or at the outermost sites of the archipelago, affect the exposure. Although a sheltered shore is indicated, the sublittoral zone may be quite exposed to the movements of water. In contrast, in an open shore environment underwater rocks, boulders and shallow water areas can provide sheltered habitats. The depth range of the F. vesiculosus belt exhibited two distinctive patterns. At sheltered sites, around islands in the outermost reaches of the archipelago F. vesiculosus can grow to a maximum depth of 5 m. In exposed habitats the belt becomes narrower, reaching a maximum depth of 3 m. Closer to the mainland F. vesiculosus is found at exposed sites to a maximum depth of 5 m; the depth range at sheltered sites is narrower, only reaching depths of 2 m or less. In conclusion, the changes in plant morphology and in the vertical belt distribution are similar to each other along both gradients at the exposed ends of the wave action spectrum; however, the two gradients diverge at the sheltered ends of the spectrum. Received: 10 August 1998 / Accepted: 11 January 1999     

Distribution and maximum growth depth of Fucus vesiculosus along the Gulf of Finland

 A survey of the distribution and maximum depth of a continuous Fucus vesiculosus belt was carried out in the Gulf of Finland in 1991. F. vesiculosus is widely distributed throughout the Gulf of Finland, including the vicinity of Vyborg Bay, Russia in the east. The maximum growth depth of F. vesiculosus in the Gulf of Finland reflects two different patterns according to the exposure to wave action. The most robust and continuous F. vesiculosus belt is observed on exposed shores, where the maximum growth depth is 5 to 6 m, with the optimum at 2 to 3 m. On moderately exposed shores the maximum growth depth is 3 m, with an optimum growth depth of <2 m. The maximum growth depth also varies geographically, with a decreasing trend towards the east. Maximum growth depth of F. vesiculosus correlates with light intensity. The compensation point for F. vesiculosus photosynthesis is about 25 μmol m⁻² s⁻¹, and photosynthesis is saturated at a light intensity of 300 μmol m⁻² s⁻¹. Vertical irradiance attenuation measurements in situ in summer revealed that for F. vesiculosus photosynthesis the quantity of light is optimal (200 to 300 μmol m⁻² s⁻¹) at <3 m depth. At depths >5 m the quantity of light is near or below the photosynthesis compensation point and insufficient for growth. These depth limits of light penetration coincide with measured growth depths of F. vesiculosus in the Gulf of Finland. Received: 7 May 1999 / Accepted: 18 November 1999     

Aquatic photochemistry of paracetamol in the presence of dissolved organic chromophoric material and nitrate

Purpose

This study contains some new findings connected to the photolysis of the drug paracetamol (hereinafter APAP) especially in light of estimating natural conditions, and it will offer information to better evaluate environmental problems connected with this widely used analgesic agent. Only a few studies, so far, have focussed on the photodegradation process of APAP in the natural environment, and the question about the role of the colored/chromophoric dissolved organic matter (CDOM) and nitrate (NO ₃ ^? ) as photoinductors is almost open.

Methods

APAP dissolved in freshwater and pure laboratory water in the presence and absence of CDOM and NO ₃ ^? ions was irradiated using weak-energy photon energies simulating natural conditions.

Results

CDOM and NO ₃ ^? as photoinductors produced only the slow phototransformation of APAP under weak energy radiation, and APAP seemed to be practically resistant to direct photolysis under weak radiant energies available in natural conditions. The estimated reaction efficiencies, in addition to half-lives, speak for that NO ₃ ^? and CDOM do not act as quite independent photoinductors but their effect in conjunction (CDOM?CNO ₃ ^? ?Cwater) is stronger than the separate ones. The principal phototransformation intermediates of APAP were mono-hydroxy derivatives, depending on available photon energies formed via ortho- or meta-hydroxylation, possessing substantial power of resistance to further specific transformation reactions.

Conclusions

The estimated half-life of the phototransformation of APAP in the natural aqueous environment and in the presence of suitable photoinductors will be about 30?days or more.