Identification of surrogate compounds for the emission of PCdd/F (I-TEQ value) and evaluation of their on-line real-time detectability in flue gases of waste incineration plants by REMPI-TOFMS mass spectrometry

Correlations between products of incomplete combustion (PIC), e.g., chloroaromatic compounds, can be used to characterise the emissions from combustion processes, like municipal or hazardous waste incineration. A possible application of such relationships may be the on-line real-time monitoring of a characteristic surrogate, e.g., with Resonance-Enhanced Multiphoton Ionization-Time-of-Flight Mass Spectrometry (REMPI-TOFMS). In this paper, we report the relationships of homologues and individual congeners of chlorinated benzenes (PCBz), dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and phenols (PCPh) to the International Toxicity Equivalent (I-TEQ) of the PCDD/F (I-TEQ value) in the flue gas and stack gas of a 22 MW hazardous waste incinerator (HWI). As the REMPI detection sensitivity is decreasing with the increase of the degree of chlorination, this study focuses on the lower chlorinated species of the compounds mentioned above. Lower chlorinated species, e.g., chlorobenzene (MCBz), 1,4-dichlorobenzene, 2,4,6-trichlorodibenzofuran or 2,4-dichlorophenol, were identified as I-TEQ surrogates in the flue gas. In contrast to the higher chlorinated phenols, the lower chlorinated phenols (degree of chlorination <4) were not reliable as surrogates in the stack gas. The identified surrogates are evaluated in terms of their detectability by REMPI-TOFMS laser mass spectrometry. The outcome is that MCBz is the best suited surrogate for (indirect) on-line measuring of the I-TEQ value in the flue gas by REMPI-TOFMS. The correlation coefficient r of the MCBz concentration to the I-TEQ in the flue gas was 0.85.     

PCBs and PCDD/Fs in lake sediments of Grosser Arbersee, Bavarian Forest, South Germany

Despite their environmental importance, there are still relatively few historical studies of the environmental occurrence of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), especially in middle Europe. Trends in PCBs and PCDD/Fs were, therefore, assessed in lake sediments of the Grosser Arbersee over the past 130 years (1860-1990). Ballschmiter-PCB concentrations (congeners # 28, 52, 101, 138, 153, 180) increased between 1946 and 1972 from 4.2 to 32.0 microg kg(-1) dry wt, but have since decreased to 25.6 microg kg(-1) dry wt. High chlorinated PCB congeners reached their maxima earlier (1968-1972) than low chlorinated congeners (1985-1991). These trends were consistent with patterns expected from the production and use of PCBs and their precursors. PCDD/F concentrations increased between 1950 from 0.6 microg kg(-1) dry wt to 2.3 microg kg(-1) dry wt in 1977, falling to 1.7 microg kg(-1) dry wt by 1993. PCDF concentrations exceeded those of PCDD until 1968, but afterwards PCDDs (especially OCDD) were predominant. These patterns suggest that domestic heating and waste combustion were the most likely sources, but pollution from local industries, such as metal smelting and glass production, might also have been involved. The data provide a valuable case study from central Europe which confirms the overall declining trends of PCB and PCDD/F contamination shown elsewhere.     

Reproduction disturbances of Brachionus calyciflorus (rotifer) for the screening of environmental endocrine disrupters

Rotifers and especially the Brachionus calyciflorus species have already shown advantages (e.g. good sensitivity, simplicity, ecological relevance, short generation time) for the chronic toxicity assessment of water pollutants. In this study, the B. calyciflorus three-day test was evaluated on ethinylestradiol, nonylphenol and testosterone for the determination of endocrine disrupting (reproductive) effects. Reproduction (intrinsic rate of population increase) and sex ratio (males/females and mictic females/amictic females) were explored and discussed as suitable endpoints. B. calyciflorus has shown a fair sensitivity to detect reproductive disrupting effects after exposure to ethinylestradiol, nonylphenol and testosterone. Population growth (intrinsic rate of population increase, r) and the ratio ovigerous females/non-ovigerous females are both suitable endpoints, whereas the occurrence of males was not frequent enough to be used as endpoint.     

Photolysis of polycyclic aromatic hydrocarbons adsorbed on spruce [Picea abies (L) Karst] needles under sunlight irradiation

Photolysis of polycyclic aromatic hydrocarbons (PAHs) sorbed on surfaces of spruce [Picea abies (L.) Karst.] needles under sunlight irradiation was investigated. PAHs were produced by combustion of polyvinyl chloride (PVC), wood, high-density polyethylene (HDPE), and styrene in a stove. The factors of sunlight irradiation on the surfaces of spruce needles were taken into consideration when investigating the kinetic parameters. The photolysis of the 18 PAHs under study follows first-order kinetics. The photolysis half-lives range from 15 h for dibenzo(a,h)anthracene to 75 h for phenanthrene. Photolysis of some PAHs on surfaces of spruce needles may play an important role on the fate of PAHs in the environment.     

Toxic emissions during co-combustion of biomass-waste wood-lignite blends in an industrial boiler

The objectives of this work were to study the PCDD/F emissions during the co-combustion of waste wood/coal co-combustion in an industrial boiler and to determine the relation of the toxic emissions to the fuel properties. Co-combustion experiments were performed in a 13.8 MWthermal industrial moving grate combustor. The fuels which were examined in this study included Greek lignite, natural uncontaminated wood, power poles and medium density fibers (MDFs) which were by-products of the plant production process. Fuel blends were prepared by mixing single components in various concentrations. PCDD/F emissions were collected during experimental runs and were analyzed according to standard methods. Low PCDD/F emissions were obtained during the co-combustion tests, lower than the limit value of 0.1 ng TEQ/Nm3. The lowest values were observed during the combustion of fuel blends containing MDF, possibly due to the inhibitory action of some of the N-containing MDF ingredients, such as urea. No direct correlation was found between the PCDD/F and the copper emissions, while examination of the PCDD/F homologue patterns revealed the predominance of the lower chlorinated isomers over the higher ones.     

Verteilungskoeffizienten chlorierter Kohlenwasserstoffe zwischen Muskulatur und Leber bei Fischen

Zusammenfassung  Lipidbezogene Verteilungskoeffizienten (KL_M/L) zwischen Muskelkonzentrationen-(C_ML) und Leberkonzentrationen (C_LL) zweier Friedfischarten Brassen (Abramis brama) und Aalmutter (Zoarces viviparus) ergeben theoriekonform (KL_M/L=C_ML/C_LL=1) nominale Werte um 1 für persistente (hochchlorierte PCB) und Werte über 1 für metabolisierbare lipophile Umweltchemikalien wie chlorierte Cyclohexane oder DDT.      

Langfristige in situ-messungen zum sauerstoffgaswechsel benthischer meerespflanzen in einem kontinuierlich registrierenden durchflußsystem

Most in situ gas-exchange measurements in aquatic organisms are still performed in closed systems (bottle method, bell-jar experiments). The disadvantages of these methods are that insufficient water movement (turbulence) or relatively long-lasting exposure periods result in under- or oversaturation phenomenas. To avoid these disadvantages as far as possible, an open, continuously recording flow-through system, employing O₂-electrodes, was devised and tested. Examples are provided of O₂-exchange recording in Fucus vesiculosus from the Baltic Sea.

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Aus dem SFB 95, Kiel.     

Erfassung der strömungsstruktur im substratbereich mariner biotope

In the phytobenthos, exchange of matter is essentially controlled by turbulent water movement. On the other hand, the phytobenthos itself alters properties of the hydrodynamic boundary layer. This paper describes experiments performed and results obtained on water movement in the substrate. Using a special hot-wire microprobe and a computer-compatible measuring device, a preliminary experimental tank model has been set up. The model species is the alga Scytosiphon lomentaria.     

Attributional conflict between managers and subordinates: An investigation of leader-member exchange effects

The present study investigated the discrepancies, or conflict, between the attributions of leaders and members as a function of LMX quality and explored the relation between attributional conflict and subordinate job satisfaction, perceptions of equity, and turnover intentions. Data for the study were provided by 141 supervisor-subordinate dyads from the managerial ranks of a large manufacturing organization. Both parties of the dyad made attributions for subordinate loyalty, affect, and contributions, member behaviors identified as critical in previous LMX research. Limited support emerged for the hypothesis that attributional conflict would be greater in dyads where subordinates reported lower rather than higher LMX quality. Findings suggested that attributional discrepencies are due, in part, to the tendency of leaders to make more favorable attributions for subordinates reporting higher LMX quality than for subordinates reporting lower LMX quality. Results also revealed that, while attributional conflict was negatively related to subordinate satisfaction and perceptions of equity and positively related to turnover intentions, attributional conflict did not predict subordinate work outcomes when the effects of LMX quality were controlled. Implications of these findings were discussed.