PCDD/F, PAH and heavy metals in the sewage sludge from six wastewater treatment plants in Beijing, China

In order to better understand land application of sewage sludge, the characterization of heavy metals, PCDD/F and PAHs in sewage sludge was investigated from six different wastewater treatment plants (WWTP) in Beijing City, China. It was found that the total concentrations of Zn in Wujiacun (WJC) sewage sludge, and Cd and Hg in sewage sludge generated from all of the six different places are higher than Chinese regulation limit of pollutants for sludge to be used for agriculture (GB18918-2002). The levels of 16 PAHs that have been categorized as priority pollutants by US EPA in the sewage sludge samples varied from 2467 to 25923 microg/kg (dry weight), the highest values of 25923 microg/kg being found in WJC WWTP. The concentrations of Benzo[a]pyrene were as high as 6.1mg/kg dry weight in WJC sewage sludge, exceeding the maximum permitted content by GB18918-2002. Individual PAH content varies considerably with sewage samples. The ratios of anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indene[1,2,3-cd]pyrene to indene[1,2,3-cd]pyrene plus benzo[g,h,i]perylene (In/In+BP), and fluoranthene to fluoranthene plus pyrene (Fl/Fl+Py) suggest that petroleum and combustion of fossil fuel were the dominant contributions for the PAHs in sewage sludge. The concentrations of total PCDD/F in the sewage sludge ranged from 330 to 4245 pg/g d.w. The toxicity equivalent concentrations is between 3.47-88.24 pg I-TEQ according to NATO/CCMS, which is below Chinese legislation limit value proposed for land application. The PCDD/F congener/homologue profiles found in the Beijing samples indicated that the high chlorinated PCDD/F contamination might originate mainly from PCP-related source and depositional sources while the low chlorinated PCDD/F homologues could be originating from incineration or coal combustion. The major source of PCDD/Fs in Beijing sludge is still unclear.     

Increased PCDD/F formation in the bottom ash from fires of CCA-treated wood

Bottom ash that was the result of the combustion of chromated copper arsenate (CCA) treated wood under controlled fire conditions showed an increase of several orders of magnitude in the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), compared to that of untreated timber. Wood that has been pressure treated with CCA contains copper (II), which is known to catalyse the so-called de novo formation of PCDD/Fs. Comparable levels of PCDD/Fs would be expected in residual ash from burning CCA-treated wood in backyard fires, stoves and wood heaters, as a consequence of similar combustion conditions.     

PCDD/F formation during thermal desorption of chlorobenzene contaminated soil

Environmental Science and Pollution Research - Unintentional formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) is observed and investigated during the thermal desorption in...     

Myeloperoxidase-catalyzed formation of PCDD/F from chlorophenols

Chlorophenols (CP) are transformed in vitro to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) by a biochemical-catalyzed oxidation. This is shown for 2,4,5-tri-, 2,3,4,6-tetra-and pentachlorophenol with myeloperoxidase recovered from human leucocytes in the presence of hydrogen peroxide. The yield, the reaction, and the PCDD/F-pattern found depend on the CP. The formation rates are in the micromol-per-mol range for all substrates. The experiments confirm the suspicion that a biochemical formation of PCDD/F from precursors such as CPs can take place in the human body and that this metabolic pathway may lead to a higher inner exposure with PCDD/F than is now assumed.     

Influence of start-up on PCDD/F emission of incinerators

This study aims to evaluate the influence of start-up on polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) concentration in the stack flue gas of incinerators and its contributing PCDD/F emission. The PCDD/F emission of the first sample among three consecutive stack flue gas samples of five intermittent incinerators, which sampled at a stable combustion condition after start-up, is 2-3 times higher than the mean of the others. For verifying the PCDD/F characteristics of incinerators during start-up, one continuous MSWI was investigated for two years. The elevated PCDD/F emissions of the MSWI during start-up could reach 96.9 ng I-TEQN m(-3) and still maintained a high PCDD/F emission (40 times higher than the Taiwan emission limit) even 18 h after the injection of activated carbon, indicating the memory effect. Taking the MSWI for example, which consists of four incinerators, the estimated annual PCDD/F emission from normal operational conditions was 0.112 g I-TEQ. However, one start-up procedure can generate approximately 60% of the PCDD/F emissions for one whole year of normal operations. And the PCDD/F emission, which is the result of the start-ups of four incinerators, was at least two times larger than that of a whole year's normal operations, without consideration for the PCDD/F emission contributed by the long lasting memory effect.     

Influence of variation in the operating conditions on PCDD/F distribution in a full-scale MSW incinerator

Optimizing the operating parameters to minimize polychlorodibenzo-p-dioxins and polychlorodibenzofurans (PCDD/F) emission is the common interest of the municipal solid waste (MSW) incineration industry. In this study, we investigated the distribution of tetra- to octa-CDD/F along the flue gas line in a full-scale reciprocating grate incinerator and evaluated the effects of temperature control and O(2) level on PCDD/F formation. Six runs were laid out and all performed under sufficient burning conditions, in which the combustion efficiency of MSW was more than 99.9%. The total concentration of tetra- to octa-CDD/F measured at the boiler outlet showed an increasing tendency with the increase of boiler outlet temperature (T(B)) from 214 degrees C to 264 degrees C. When flue gas ran across the semi-dry scrubber and cyclone precipitator, in which the temperature varied from 264 degrees C to 162 degrees C, the concentrations of the lower chlorinated dioxins and furans were significantly raised, especially for the TCDF. Increasing O(2) supply from 6.0% to 10.5% essentially led to a higher yield of tetra- to octa-PCDD/F, suggested that under sufficient burning conditions the lower O(2) level was favorable for reducing PCDD/F formation and emission. The variation of O(2) level did not give rise to a systematical change of PCDD/F homologue pattern. For all measurements, the isomer distributions of tetra- to hepta-PCDD/F were more or less the same, nearly independent of variations in the operating conditions and sampling positions. Only the significant increase of the sum of 1,3,7,8-TCDF and 1,3,7,9-TCDF was found in the zone after the boiler section.     

Modeling the formation of PCDD/F in solid waste incinerators

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) appear in unacceptable amounts in the gaseous emissions during the incineration of wastes containing significant quantities of chlorine and metals, such as MSW and medical waste. They are formed both in the gas phase at temperatures above 600 degrees C and on the surface of the solid phase (flyash) in the temperature range 400-225 degrees C. Both the precursor (from existing smaller chlorinated molecules) and de novo (from elemental carbon) routes are involved. An empirically derived global model for their de novo formation on flyash in MSW and medical waste incinerators has now been extended to include the precursor mechanism, and a gas phase formation component, with separate rate expressions for PCDD and PCDF. Homogeneous PCDD formation is governed by the concentration of chlorophenols and PCDF by that of chlorophenols and chlorobenzenes. The result is more complete system which distinguishes between the gas and solid phase contributions to the I-TEQ. An additional step for the adsorption of gaseous PCDD/F back onto the solid phase during cooling suggests this should be minimal in the gas ducts of an incinerator. The extended model has been tested against experimental data collected from a well-controlled pilot incinerator and commercial incinerators, and found to adequately describe the measured outputs. With the model it should be possible to predict the PCDD/F emissions from commercial incinerators, provided that the ash properties and the overall temperature-time profiles are known.     

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.     

Influence of metal oxides on PCDD/Fs formation from pentachlorophenol

Chlorophenols (ClPhs) are considered as important precursors for PCDD/Fs formation. The influences of series of metal oxides including MgO, Al2O3, CaO, BaO, TiO2, V2O5, MnO2, Fe2O3, Co3O4, CuO, Ag2O, ZnO, HgO, SnO, PbO, La2O3, CeO2, and Eu2O3 on PCDD/Fs formation from pentachlorophenol (PCP) were investigated in a laboratory-scale reactor. The results indicated that most of the above metal oxides have obvious suppressing effects on the total amount of PCDD/Fs formation from precursor PCP except for CuO, ZnO, MnO2, TiO2 and Co3O4 with promotion effects at 280 degrees C for 2 h. Although MgO, Al2O3, Fe2O3, PbO, La2O3 and Eu2O3 could reduce the amount of octachlorinated dibenzo-p-dioxin (OCDD), they promote the formation of more toxic 1,2,3,4,6,7,8-HpCDD at the same time. The total suppressing efficiencies of several metal oxides including CaO, BaO, PbO, Ag2O, HgO and SnO which have lower Z/r (charge to radius ratio) <2 are all over 90%. The theories of generalized acid-base and atomic parameter (Z/r) were used to speculate the effecting mechanisms. The factors including time and temperature on suppressing efficiencies of CaO, BaO and PbO have also been studied in the present paper. The results showed that the total suppressing efficiencies of CaO, BaO and PbO increase with the increase of heated time and temperature.     

Surface contamination with PASH, PAH and PCDD/F after fire accidents in private residences

Surface samples were taken from two private residences after real fire accidents. The goal was, to determine the surface contaminations with polycyclic aromatic sulfur heterocycles (PASH), as representatives of a substance class, not investigated in this context, by now, polycyclic aromatic hydrocarbons (PAH) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). Analytical method for the determination of PASH was developed for the respective matrix. Concentrations measured ranged between 1.70 and 465 micrograms/m2 for PASH, 34.3 and 58,800 micrograms/m2 for PAH (EPA), and 4.15 and 1,300 ng/m2 for PCDD/F, as well. Obviously, PASH were formed during the fire accidents. Nevertheless, PAH were the most relevant pollutants after these small fires.     

CuCl2-catalyzed PCDD/F formation and congener patterns from phenols

Homologue and isomer patterns of polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) in CuCl2-catalyzed formation were studied in an isothermal flow reactor using a distribution of 20 phenols as measured in municipal waste incinerator (MWI) exhaust gases. A mixture of 20 phenols was synthesized and used as reactants for this study because phenols are known to be key precursors in the formation of PCDD/F. Experiments were conducted at 400 degrees C. The 92% of nitrogen (N2) and 8% of oxygen (O2) were used as a carrier gas. PCDD/F homologue and isomer patterns with dibenzo-p-dioxin (DD) and dibenzofuran (DF) were obtained from a mixture of 20 phenols. DF+PCDF formation was favored over DD+PCDD formation. The major homologue groups formed were non-chlorinated DD and DF, and PCDD/F homologue fraction decreased with the degree of chlorination. PCDD/F homologue and isomer distributions were almost constant. Phenol and lower chlorinated phenols present in high amount played an important role in PCDD/F congener distributions. The results presented here can be used as characteristics or fingerprints for homologue and isomer patterns of PCDD/F formation attribution in CuCl2-catalyzed reaction from phenols.     

Transient behavior of heavy metals in soils during electrokinetic remediation

This paper presents a systematic bench-scale laboratory study performed to assess the transient behavior of chromium, nickel, and cadmium in different soils during electrokinetic remediation. A series of laboratory electrokinetic experiments was conducted using two different clayey soils, kaolin and glacial till. For each type of soil, four electrokinetic experiments with 1, 2, 4, and 10 d of treatment time were performed. In all tests, the contaminants were Cr(VI), Ni(II), and Cd(II) combined in the soil. A geochemical assessment was performed using the geochemical model MINEQL(+) to determine the partitioning of the heavy metals in soils as precipitated, adsorbed, and aqueous forms. Results showed that in kaolin, the extent of Ni(II) and Cd(II) migration towards the cathode increased as the treatment time increased. Unlike kaolin, in glacial till treatment time had no effect on nickel and cadmium migration because of its high buffering capacity. In both kaolin and glacial till, the extent of Cr(VI) migration towards the anode increased as the treatment time increased. However, Cr(VI) migration was higher in glacial till as compared to kaolin because of the high pH conditions that existed in glacial till. In all tests, some Cr(VI) was reduced to Cr(III), and the Cr(VI) reduction rate to Cr(III) as well as the Cr(III) migration were significantly affected by the treatment time. Overall, this study showed that the electroosmotic flow as well as the direction and extent of contaminant migration and removal depend on the polarity of the contaminant, the type of soil, and the treatment duration.     

Environmental prospection for PCDD/PCDF, PAH, PCB and heavy metals around the incinerator power plant of Reggio Emilia town (Northern Italy) and surrounding main roads

Samples of soil, sediment and pine needles from the Reggio Emilia area were analysed in order to estimate the environmental pollution caused by an MSWI. PCDD/PCDF, PCB, PAH and metals were analysed in the collected samples. The data obtained showed relatively low pollution levels. Indeed, the PCDD/PCDF and PCB data were comparable to the values usually found in the grazing areas of the European Union countries. Metal concentrations in soils and sediments may be related to local geological occurrences and to agricultural activities. PAH values are significantly lower than the limit values set by the Italian law.     

A simple kinetic model of PCDD/F formation by de novo synthesis

A simple fixed-bed reactor model is used to describe experimental data about the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) from fly ash carbon. The heterogeneous oxidation of graphite-like carbon is represented by a reaction which is first order in carbon and one half order in oxygen. The same orders of reaction are assumed to be valid for PCDD/F formation, such that the oxidation of fly ash carbon would have three parallel channels leading to COx, PCDD and PCDF. In addition, PCDD/F degradation by oxygen is considered and appropriate rate constants were fitted to simulate the experimental data. The effects of water vapour and particulate copper on PCDD/F formation are included. As a result, an overall kinetic model of PCDD/F formation is obtained which describes most of the experimental data with reasonable accuracy. The main reaction channel, COx formation, needs to be understood more completely, in order to interpret PCDD/F reaction pathways better. The model can be extended to include other chlorinated aromatics and the gas/particle partitioning of the semivolatiles. It provides a basis for the qualitative and quantitative interpretation of fixed-bed and flow reactor results and it is hoped to be applicable to industrial installations like waste incinerators and metal smelters.     

Influence of heavy metals on the microbial degradation of diesel fuel

The degradation of diesel fuel by a microbial community from a soil polluted by heavy metals (h.m.) in the presence of Cu, Ni, Zn, Pb, Cd, Hg and Cr (as chromate) was investigated. Experiments were conducted with soil slurries and the extracted community in liquid cultivation. The concentrations applied were in the sub-mM and mM range. Whereas the slurries displayed no significant effect, degradation in liquid culture was increasingly inhibited by higher metal concentrations. The course of degradation in suspension was demonstrated by the oxygen consumption. The order of toxicity was found to be: Hg > Cr(VI) > Cu > Cd > Ni > Pb > Zn. The absence of any effect for slurries was due to the non-availability of the metals in the soil, and to precipitation or adsorption to the soil in the case of amendment. The paper also includes results on the availability of h.m. and changes to the community after exposure.     

PCDD/F and PCB in spruce forests of the Alps

PCDD/F and PCB concentrations in remote mountainous spruce stands of the Central European Alps show strong geographic variation. Independent of the matrix (0.5 year old needles, humus or mineral soil), the highest pollutant levels were always found at the lateral zones of the mountain range. High levels coincided with strong precipitation, particularly along the northern margin of the study region. The most volatile PCB congener propagated farther into the colder, drier central Alps than the heavier species. Matrices with different accumulation history (needles and humus) repeatedly reflected different spatial immission patterns. Consistent with its much longer exposure, pollutant levels in humus exceeded those of needles by up to two orders of magnitude. Needle contamination varied with altitude but the vertical trends were highly variable between transsects and changed between years, too.     

The PCDD/F and PBDD/F pollution in the ambient atmosphere of Shanghai, China

Rapid economic growth in the last two decades in Shanghai has had a great adverse influence on its air quality. Therefore, the atmospheric pollutants of Shanghai have received much concern. In this study, concentrations of 2,3,7,8-substituted PCDD/Fs and PBDD/Fs congeners were measured in the ambient air of four districts in Shanghai. The mean atmospheric concentrations (TEQs) of total 2,3,7,8-PCDD/Fs and 2,3,7,8-PBDD/Fs were 8031 fg m(-3) (497.1 fg I-TEQ m(-3)) and 1358 fg m(-3) (304.1 fg I-TEQ m(-3)) for Jiading District, 5308 fg m(-3) (289.0 fg I-TEQ m(-3)) and 709 fg m(-3) (146.9 fg I-TEQ m(-3)) for Zhabei District, 4014 fg m(-3) (144.4 fg I-TEQ m(-3)) and 1239 fg m(-3) (256.9 fg I-TEQ m(-3)) for Pudong District, 3348 fg m(-3) (143.2 fg I-TEQ m(-3)) and 699 fg m(-3) (148.4 fg I-TEQ m(-3)) for Huangpu District, respectively. Our results showed that almost all the PCDD/Fs and PBDD/Fs congeners were partitioned into the particulate phase except the lower chlorinated or brominated ones. The logarithm of the gas/particle partitioning coefficient K(p) has good linear correlation with that of the sub-cooled vapor pressure p(L). Concentrations of PCDD/Fs and PBDD/Fs were both positively correlated to elemental carbon in all districts except Pudong District, suggesting elemental carbon could be a good indicator for dioxins' air pollution. It is intensively suggested that more detailed and deeper studies about PBDD/Fs should be carried out due to their relatively high atmospheric concentrations in Shanghai.     

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.