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.     

Effects of a catalytic converter on PCDD/F, chlorophenol and PAH emissions in residential wood combustion

Temporal variations in concentrations of perfluorinated carboxylic acids (PFCAs) and sulfonic acids (PFSAs), including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) structural isomers, were examined in livers of pilot whale (Globicephala melas), ringed seal (Phoca hisida), minke whale (Balaenoptera acutorostrata), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata), Atlantic white-sided dolphin (Lagenorhynchus acutus) and in muscle tissue of fin whales (Balaenoptera physalus). The sampling spanned over 20 years (1984-2009) and covered a large geographical area of the North Atlantic and West Greenland. Liver and muscle samples were homogenized, extracted with acetonitrile, cleaned up using hexane and solid phase extraction (SPE), and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). In general, the levels of the long-chained PFCAs (C9-C12) increased whereas the levels of PFOS remained steady over the studied period. The PFOS isomer pattern in pilot whale liver was relatively constant over the sampling years. However, in ringed seals there seemed to be a decrease in linear PFOS (L-PFOS) with time, going from 91% in 1984 to 83% in 2006.     

Correlation between PCDD/F, PCB and PCBz in coal/waste combustion. Influence of various inhibitors

In the flue gas of co-combustion of solid waste and coal in a laboratory scale furnace high concentrations of polychlorinated dibenzo-p-dioxin and furans (PCDD/F), polychlorinated biphenyls (PCB) and polychlorinated benzenes (PCBz) have been detected. These toxic emissions have been reduced by the help of various inhibitors added to fuel before incineration. Knowledge of the congener pattern and homologue profiles of PCDD/F, PCB and PCBz is important to elaborate the mechanism of formation and inhibition of the toxic compounds formed during co-combustion of solid waste and coal. Principle component analysis (PCA) is used in order to find the similarity between the samples and separate them according their toxicity. By the help of the component analysis (CA) the best correlated congeners are effectively detected. Using linear regression between the independent variables and the indicator parameters various good correlated pairs between PCDD/F, PCB and PCBz have been elaborated. Generally it was found that the samples with higher toxicity show a good correlation between tetra- and pentachlorinated benzenes and tetra- and pentachlorinated dibenzo-p-furans. The best indicator parameter for PCDD/F World Health Organization toxic equivalent (WHO-TEQ) among the PCBz congeners investigated is 1,2,4,5-TCBz. This isomer is also significantly correlated with PCDD/F WHO-TEQ and with the sum of PCDD/F WHO-TEQ and PCB WHO-TEQ. However for samples with higher percentage of inhibitors the above mentioned relationship between the surrogate and WHO-TEQ disappeared. The PCB homologues and congeners show no correlation with PCBz and PCDD/F homologues and congeners.     

Relationship of PCDD/F and Co-PCB concentrations in breast milk with infant birthweights in Tokyo, Japan

OBJECTIVE: To observe how PCDD/F and Co-PCB concentrations in breast milk relate to infant birthweights in Tokyo, Japan. STUDY DESIGN: Breast milk samples were collected from 240 mothers (aged 25-34years old) residing in Tokyo to measure the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs; 14 congeners), polychlorinated dibenzofurans (PCDFs; 15 congeners), and coplanar polychlorinated biphenyls (Co-PCBs; 12 congeners) in the breast milk fat. Individual milk samples (about 50ml) were obtained 30days after delivery, between the months of June and September in 1999 and 2000. The relationship of the infant birthweights with the PCDD/F and Co-PCB concentrations was observed. RESULTS: The birthweights were negatively correlated the concentrations of many of the PCDD/F and Co-PCB congeners, with the mean toxic equivalent quantities (TEQs) of the Co-PCBs, and with the sum of the PCDD, PCDF and Co-PCBs, although their correlation coefficients were less than 0.200. Multiple regression analysis showed octachlorodioxin was statistically significant explanatory variate. CONCLUSIONS: There were slight relationship between the dioxins levels of breast milk and the birthweights of the infants.     

Evaluation of PCDD/F oxidation catalysts: confronting studies on model molecules with tests on PCDD/F-containing gas stream

Titania supported vanadium oxide is a renowned catalyst for the abatement of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from gas effluents. To develop more active formulations, researchers mainly rely on lab-scale experiments on “PCDD/Fs-mimicking substances”, like (chloro)-benzene. Using such model compounds is convenient whereas handling PCDD/Fs in the laboratory is potentially hazardous and complicated. Recent studies, however, challenged some foremost conclusions of model compound based studies, starting from the observation that different model compounds gave contrasted results. Thus the present work aims at confronting some of these dubious conclusions with direct experimental tests on PCDD/Fs. One reference V₂O₅/TiO₂ catalyst and three modified formulations (V₂O₅/TiO₂-SO₄, V₂O₅-MoO₃/TiO₂, and V₂O₅-WO₃/TiO₂) have been evaluated. A dedicated apparatus was used which allows safe and reliable tests on a mixture of PCDD/Fs congeners. Some of the previously proposed catalyst improvement strategies actually prove to be disadvantageous in the removal of PCDD/Fs. In particular, MoO₃- and WO₃-modified catalysts were significantly less active than the reference catalyst. These observations show that conclusions from model compound based studies must be drawn with care and should ideally be confronted with tests on the actual target pollutants.     

Effect of dissolved humic matters on the leachability of PCDD/F from fly ash--laboratory experiment using Aldrich humic acid

The effect of dissolved humic matters (DHM) on the leachability of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) in fly ash was studied theoretically and in laboratorial condition to verify the previous results for pilot and field experiment of incineration residues landfill. In theoretical review, it was shown that DHM could influence the actual solubility and leachability of PCDD/F. The higher concentration of DHM showed the higher leachability of PCDD/F. In the leaching test, three different DHM concentrations and pHs of solutions were adopted to fly ash samples imaging the various characteristics of municipal solid waste leachate. It was proved experimentally that the leachability of PCDD/F increased with increasing DHM concentration in all pH conditions. The highest leachability was shown at the highest pH. Isomer distribution patterns of PCDD/F in all leachates were similar in all pH conditions. It backed up the distribution theory of PCDD/F between DHM and water.     

Mechanistic studies on the role of PAHs and related compounds in PCDD/F formation on model fly ashes

Model fly ashes containing Florisil, CuCl2.2H2O and PAHs with structures similar to dibenzo-p-dioxin or dibenzofuran were heated at 250 degrees C in He/O2 with regard to a supposed intramolecular reaction mechanism for oxygen incorporation. Highest reactivities in PCDF formation could be found for model compounds containing a biphenyl structure, while condensed pi-systems lead to a decrease in reactivity for such compounds. Biphenyl is almost completely converted to dibenzofuran. PCDD formation from six-membered rings like xanthene/9,10-dihydroanthracene is of minor importance. 18O-labeling of gaseous oxygen reveals no common reaction step for oxygen incorporation using 9-fluorenone, xanthene, diphenyl ether and diphenyl-2-carboxylic acid as model compounds. Pre-existing oxygen in reactants is a major source for ether groups in PCDD and PCDF. Determination of labeled and unlabeled CO and CO2 besides He/O2 reflects higher reactivities towards oxidation for model compounds containing ether groups than for compounds with carbonyl groups.     

Prediction of PM10 concentrations at urban traffic intersections using semi-empirical box modelling with instantaneous velocity and acceleration

At urban traffic intersections, vehicles frequently stop with idling engines during the red-light period and speed up rapidly during the green-light period. The changes of driving patterns (i.e., idle, acceleration, deceleration and cruising patterns) generally produce uncertain emission. Additionally, the movement of pedestrians and the influence of wind further result in the random dispersion of pollutants. It is, therefore, too complex to simulate the effects of such dynamics on the resulting emission using conventional deterministic causal models.For this reason, a modified semi-empirical box model for predicting the PM₁₀ concentrations on roadsides is proposed in this paper. The model constitutes three parts, i.e., traffic, emission and dispersion components. The traffic component is developed using a generalized force traffic model to obtain the instantaneous velocity and acceleration when vehicles move through intersections. Hence the distribution of vehicle emission in street canyon during the green-light period is calculated. Then the dispersion component is investigated using a semi-empirical box model combining average wind speed, box height and background concentrations. With these considerations, the proposed model is applied and evaluated using measured data at a busy traffic intersection in Mong Kok, Hong Kong. In order to test the performance of the model, two situations, i.e., the data sets within a sunny day and between two sunny days, were selected to examine the model performance. The predicted values are generally well coincident with the observed data during different time slots except several values are overestimated or underestimated. Moreover, two types of vehicles, i.e., buses and petrol cars, are separately taken into account in the study. Buses are verified to contribute most to the emission in street canyons, which may be useful in evaluating the impact of vehicle emissions on the ambient air quality when there is a significant change in a specific vehicular population.     

Influence of heavy metals on the formation and the distribution behavior of PAH and PCDD/F during simulated fires

Combustion experiments were performed with an artificial fire load (polystyrene and quartz powder) in a laboratory scale incinerator in the presence of gaseous HCl to simulate accidental fire conditions. The aim of this investigation was to trace back the alterations of the formation and the distribution behavior of PAH and PCDD/PCDF to the presence of CuO or a mixture of metal oxides (CdO, CuO, Fe(2)O(3), PbO, MoO(3), ZnO). The total amount of the 16 PAH target compounds was reduced by the factor of 5-9 when the mixture of metal oxides was present rather than merely CuO. PAH patterns as well as their distribution behavior were significantly influenced by these oxides. In general, transportation inside the installation was enhanced for most of the 16 analyzed PAH. Only fluorene and dibenzo[a,h]anthracene were transported to a smaller extent. In contrast to PAH, total concentrations of PCDD were increased by factor 9 and of PCDF by factor 10, respectively, when CuO was present. Adding the mixture of metal oxides resulted in an increase of PCDD by factor 14 and of PCDF by factor 7. CuO and the mixture of metal oxides had a different influence on the PCDD/F homologue patterns. For instance, the HxCDF to OCDF ratio after incineration without any metal oxide was 1 to 6, whereas addition of CuO or the mixture of the metal oxides shifted the HxCDF to OCDF ratios towards 1 to 40 or 1 to 17, respectively. Combustion along with CuO increased transportation of higher chlorinated PCDF congeners, whereas the mixture of the metal oxides caused a strong decrease of PCDF distribution throughout the system.     

Laboratory studies on formation and minimisation of polychlorinated dibenzodioxins and -furans (PCDD/F) in secondary aluminium process

The objectives of this work were to study the formation mechanisms of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) in thermal aluminium recycling processes by use of laboratory experiments. The pattern of isomers of PCDD/F indicates that de novo synthesis is important in aluminium smeltery. The mechanisms of PCDD/F formation in aluminium smelting are similar to that of various incineration processes of waste material. The results of bioanalysis (EROD-test) confirms the existence of de novo synthesis of PCDD/F, but points out to the existence to some additional, toxic compounds of unknown structure. To reduce the amount of PCDD/F the input of carbon at the metal should be reduced; in addition the metal smeltery plants should be cleaned from fly ash particles. It is suggested to use good primary methods in the technical plants like constant feeding of the metal into the oven will minimise PCDD/F concentration. The biological EROD-bioassay is a good tool to estimate PCDD/F-TEQ values also for this technical process simulated in the laboratory.     

Quantification of PCDD/F concentrations in animal manure and comparison of the effects of the application of cattle manure and sewage sludge to agricultural land on human exposure to PCDD/Fs

PCDD/Fs were quantified in samples of cattle, pig, sheep and chicken manure. TEQs ranged from 0.19 ng TEQ/kg dw for the pig manure to 20 ng TEQ/kg dw for one cattle manure sample. Exposure assessments were carried out to compare the effect of various sewage sludge and cattle manure land application scenarios on human PCDD/F exposure. Background exposure was estimated at 4.9 pg TEQ/kg bw/day and it was found that land application of sewage sludge and cattle manure at contemporary rates did not increase PCDD/F TEQ background exposure. It was concluded that the application of sewage sludge, under the new UK guidelines, and cattle manure to agricultural land, do not make a significant contribution to human exposure to PCDD/Fs.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

Effects of oxygen on formation of PCB and PCDD/F on extracted fly ash in the presence of carbon and cupric salt

The effect of oxygen-nitrogen atmosphere (N2 + 10%O2, N2 + 1%O2 and 99.999% N2) on the formation of PCB, PCDD and PCDF by the de novo synthetic reactions in the system consisting of extracted fly ash (from municipal waste incinerators--MWI), activated carbon, CuCl2 x 2H2O and NaCl at 340 degrees C was studied. The content of PCDD/F for systems with 10%O2, 1%O2 and 99.999% N2 was decreasing and corresponded to 17,304, 5544, and 1437 ng/sample. In all studied systems the isomer OCDD/F was prevailing. The content of PCBs in the same system was also decreasing from 1214 to 166 ng/g. Formation of nonortho PCB was relatively high compared to the system where only nitrogen was present. The possible mechanism of formation is outlined.     

Thermolysis of 2,4,6-trichlorophenol chemisorbed on aluminium oxides as example of fly ash mediated surface catalysis reaction in PCDD/PCDF formation

The influence of aluminium cation as a strong electrophilic centre on the thermolysis of chlorophenols chemisorbed on Al(OH)₃ surface was investigated. If thermolysis is carried out at 300 °C the spontaneous rupture of the bond between aluminium and oxygen of phenol takes place in the temperature range of 260–280 °C. The thermolysis of chlorophenoxy aluminium compounds occurs through homolytic and heterolytic bond cleavage. In the case of heterolytic cleavage the leaving chlorophenoxy anion causes a simultaneous formation of the aluminium cation, which is the driving force for the rearrangement of the unstable intermediate. By homolytic cleavage of the Al–O bond the chlorophenoxy radical is formed. The isolation of reaction products of the thermolysis of the system Al(OH)₃/2,4,6-trichlorophenol gave five isomers of dimeric compounds of resonance stabilised 2,4,6-trichlorophenoxy radical. The compounds are stable in nonaqueous, aprotic solution, but they are very sensitive to acid catalysis. They quickly transform into aromatic hydroxydiphenyl ethers. The process of dechlorination and aromatisation of cyclohexadienone dimers gives PCDD/PCDF.     

The impact of production type and region on polychlorinated biphenyl (PCB), polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in Canadian chicken egg yolks

Chicken eggs from five different production types (conventional, omega-3 enriched, free range, organic and free run) were collected, when available, from three regions (west, central and east) of Canada to determine persistent organic pollutant (POP) concentrations. Total polychlorinated biphenyl (PCB) concentrations (∑37 congeners) in yolks from the eggs ranged from 0.162 ng g⁻¹ lipid to 24.8 ng g⁻¹ lipid (median 1.25 ng g⁻¹ lipid) while the concentration of the sum of the 6 indicator PCBs ranged from 0.100 ng g⁻¹ lipid to 9.33 ng g⁻¹ lipid (median 0.495 ng g⁻¹ lipid). Total polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) concentrations ranged from 2.37 pg g⁻¹ lipid to 382 pg g⁻¹ lipid (median 9.53 pg g⁻¹ lipid). The 2005 WHO toxic equivalency (TEQ) ranged from 0.089 pg TEQ_{PCDD/F+dioxin-like[DL]-PCB} g⁻¹ lipid to 12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid (median 0.342 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). PCB and PCDD/F concentrations were significantly different (p < 0.001) in egg yolks from different regions of collection. In contrast to observations in Europe, PCB and PCDD/F concentrations in Canadian egg yolks were not impacted solely by the production type (e.g., conventional, free range, organic, etc.) used to maintain the laying chickens. Additionally, only one Canadian free range yolk from western Canada (12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid) exceeded the European toxic equivalent concentration limits for eggs (5 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). This differs from observations in Europe where free range/home produced eggs frequently have higher POP concentrations than eggs from other production types. Median PCB dietary intake estimates based on consumption of eggs were less than 10 ng d⁻¹ while median PCDD/F intakes were less than 45 pg d⁻¹.     

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NOx photooxidation system

High concentrations (>15 μm³ cm^?3) of CaSO₄, Ca(NO₃)₂ and (NH₄)₂SO₄ were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO_x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO₄ and aqueous Ca(NO₃)₂), even at elevated concentrations. The presence of high concentrations of (NH₄)₂SO₄ aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH₄)₂SO₄ on SOA yield is found to be positively correlated with the (NH₄)₂SO₄ surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH₄)₂SO₄ seed aerosols.     

Effect of combined nitrogen on dinitrogen fixation and productivity in Pisum sativum L. Inoculated with different strains of Rhizobium

This growth chamber study was designed to determine rates of nitrogen fixation, growth, productivity and concentrations of nitrogen and phosphorus during vegetative growth, flowering and the beginning of the fruiting and ripening period in Pisum sativum plants supplied with different concentrations of nitrate and nodulated by various strains of Rhizobium leguminosarum. Noninoculated control plants were grown under the same nutritional conditions. Nodulated and unnodulated plants responded differently to treatment. The effects of inoculation with Rhizobium and the nitrate treatments on the parameters of growth and nitrogen content varied with plant age. Although the presence of nitrate in the culture medium inhibited nodulation and acetylene reducing activity (ARA), the different Rhizobium strains used in the inoculations led to variations in tolerance to combined nitrogen.