Reductions in emissions of carbonaceous particulate matter and polycyclic aromatic hydrocarbons from combustion of biomass pellets in comparison with raw fuel burning

Biomass pellets are emerging as a cleaner alternative to traditional biomass fuels. The potential benefits of using biomass pellets include improving energy utilization efficiency and reducing emissions of air pollutants. To assess the environmental, climate, and health significance of replacing traditional fuels with biomass pellets, it is critical to measure the emission factors (EFs) of various pollutants from pellet burning. However, only a few field measurements have been conducted on the emissions of carbon monoxide (CO), particulate matter (PM), and polycyclic aromatic hydrocarbons (PAHs) from the combustion of pellets. In this study, pine wood and corn straw pellets were burned in a pellet burner (2.6 kW), and the EFs of CO, organic carbon, elemental carbon, PM, and PAHs (EF(CO), EF(OC), EF(EC), EF(PM), and EF(PAH)) were determined. The average EF(CO), EF(OC), EF(EC), and EF(PM) were 1520 ± 1170, 8.68 ± 11.4, 11.2 ± 8.7, and 188 ± 87 mg/MJ for corn straw pellets and 266 ± 137, 5.74 ± 7.17, 2.02 ± 1.57, and 71.0 ± 54.0 mg/MJ for pine wood pellets, respectively. Total carbonaceous carbon constituted 8 to 14% of the PM mass emitted. The measured values of EF(PAH) for the two pellets were 1.02 ± 0.64 and 0.506 ± 0.360 mg/MJ, respectively. The secondary side air supply in the pellet burner did not change the EFs of most pollutants significantly (p > 0.05). The only exceptions were EF(OC) and EF(PM) for pine wood pellets because of reduced combustion temperatures with the increased air supply. In comparison with EFs for the raw pine wood and corn straw, EF(CO), EF(OC), EF(EC), and EF(PM) for pellets were significantly lower than those for raw fuels (p < 0.05). However, the differences in EF(PAH) were not significant (p > 0.05). Based on the measured EFs and thermal efficiencies, it was estimated that 95, 98, 98, 88, and 71% reductions in the total emissions of CO, OC, EC, PM, and PAHs could be achieved by replacing the raw biomass fuels combusted in traditional cooking stoves with pellets burned in modern pellet burners.     

Emission factors and importance of PCDD/Fs, PCBs, PCNs, PAHs and PM10 from the domestic burning of coal and wood in the U.K

This paper presents emission factors (EFs) derived for a range of persistent organic pollutants (POPs) when coal and wood were subject to controlled burning experiments, designed to simulate domestic burning for space heating. A wide range of POPs were emitted, with emissions from coal being higher than those from wood. Highest EFs were obtained for particulate matter, PM10, (approximately 10 g/kg fuel) and polycyclic aromatic hydrocarbons (approximately 100 mg/ kg fuel for sigmaPAHs). For chlorinated compounds, EFs were highest for polychlorinated biphenyls (PCBs), with polychlorinated naphthalenes (PCNs), dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) being less abundant. EFs were on the order of 1000 ng/kg fuel for sigmaPCBs, 100s ng/ kg fuel for sigmaPCNs and 100 ng/kg fuel for sigmaPCDD/Fs. The study confirmed that mono- to trichlorinated dibenzofurans, Cl1,2,3DFs, were strong indicators of low temperature combustion processes, such as the domestic burning of coal and wood. It is concluded that numerous PCB and PCN congeners are routinely formed during the combustion of solid fuels. However, their combined emissions from the domestic burning of coal and wood would contribute only a few percent to annual U.K. emission estimates. Emissions of PAHs and PM10 were major contributors to U.K. national emission inventories. Major emissions were found from the domestic burning for Cl1,2,3DFs, while the contribution of PCDD/F-sigmaTEQ to total U.K. emissions was minor.     

Formation and control of toxic polychlorinated compounds during incineration of wastes containing polychlorinated naphthalenes

To estimate the potential impact on municipal solid waste (MSW) incinerator toxic equivalent (TEQ) emissions of treating wastes containing polychlorinated naphthalenes (PCNs), pilot-scale thermal treatment experiments were conducted. MSW (run 1) and MSW fortified with synthetic rubber belts containing PCNs (runs 2 and 3) were incinerated. Flue-gas and ash samples were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (co-PCBs), and PCNs. Final exhaust-gas WHO-TEQ emissions were all less than 0.1 ng/Nm3. Flue-gas TEQs were mainly from PCDFs (58-74%). When 2,3,7,8-tetrachlorodibenzo-p-dioxin relative potency factors (REPs) of specific PCN congeners from previous reports were used as estimated toxic equivalency factors to compute estimated PCN TEQs and total TEQs along with PCDDs, PCDFs, and co-PCBs, the contributions of PCNs to the total TEQs were small in ash samples and up to 28% in final exhaust gas. The TEQs in primary combustion flue gases increased through the formation of dioxins and PCNs and then decreased via secondary combustion, fabric filtration, and activated carbon adsorption. From this pilot-scale study, the incremental impact of incinerating PCN-containing wastes on annual TEQ emissions in Japan is estimated as 0.27 g of total TEQ.     

PCDD/F,PCB, HxCBz,PAH, and PM emission factors for fireplace and woodstove combustion in the San Francisco Bay region

Emissions from residential fireplace and woodstove appliances burning fuels available from the San Francisco Bay area were sampled for polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs), polychlorinated biphenyls (PCBs), hexachlorobenzene (HxCBz), particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs, and the monosaccharide levoglucosan. Emission factors for these pollutants were determined, the first known characterization of this extent. Common California natural firewoods and manufactured artificial logs were tested under operating conditions intended to reflect domestic use patterns in the Bay area, which are primarily episodic burning for aesthetic reasons. Emission factors were determined by fuel type, fuel weight, mass emission rates, and energy output, highlighting differences between fuel and combustion facility type. Average PCDD/F emissions factors ranged from 0.25 to 1.4 ng toxic equivalency (TEQ)/kg of wood burned for natural wood fuels and 2.4 ng TEQ/kg for artificial logs. The natural wood emission factors are slightly lower than those which had been estimated for the U.S. inventory. Background-corrected PCBs emitted from woodstove/oak combustion (8370 ng/kg) are 3 orders of magnitude higher in mass than total PCDDs/Fs; however, their toxicity (0.014 ng TEQ/kg) is significantly lower. HxCBz emission factors varied from 13 to 990 ng/kg and were likely fuel- and appliance-specific. Relative PAH concentrations of particle-phase compounds and emission factors were consistent with others' findings. A total of 32 PAH compounds, ranging in concentration from 0.06 to 7 mg/kg, amounted to between 0.12 and 0.38% of the PM mass, depending on the wood and facility type. Preliminary analyses suggest relationships between wood combustion markers and PCDD/F levels.     

Emission of PCDD/F, PCB, and HCB from combustion of firewood and pellets in residential stoves and boilers

To assess potential emissions of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and hexachlorobenzene (HCB) from residential combustion of biofuels, experiments were performed in which various types of pellets and firewood were combusted in four types of stoves and boilers, with both full and reduced rates of air supply. Intermittent combustion of wood pellets resulted in emissions of 11 ng-(WHO-TEQ)/kg combusted fuel (dry weight). A modern, environmentally certified boiler yielded somewhat lower emissions of PCCD/F and PCB than a wood stove. Both gave <0.1 ng(WHO-TEQ)/m3n (1.3-6.5 ng(WHO-TEQ)/kg) and considerably lower emissions than an old boiler (7.0-13 ng(WHO-TEQ)/kg). No positive effect on emissions could be observed in full air combustion (simulating the use of a heat storage tank) compared to combustion with reduced air. Two of the wood combustion experiments included paper and plastic waste fuels. Chlorine-containing plastic waste gave rise to high emissions: ca. 310 ng(WHO-TEQ)/ kg over the whole combustion cycle. The homologue profiles of PCDD/Fs show characteristic differences between ashes and flue gas from combustions with different levels of air supply. These differences do not, however, seem to have any correlation to the relative amount of toxic congeners.     

Formation of PCDDs,PCDFs, and coplanar PCBs from incineration of various woods in the presence of chlorides

Exhaust gases from the combustion of woods (Japanese red pine, Japanese cedar, Siebold's beech, seawater-impregnated Japanese red pine and Japanese cedar, waste woods containing chlordane, and waste woods containing pentachlorophenol) were collected at the outlet of a combustion chamber. A small-scale incinerator with a stationary grate was used. The samples were analyzed for PCDDs, PCDFs, and coplanar PCBs by gas chromatography/ mass spectrometry (GC/MS). When the grate temperature of the combustion chamber was lower than 700 degrees C, the total amount of PCDDs, PCDFs, and coplanar PCBs formed was proportional to the chlorine content of the combustion samples. On the other hand, when the grate temperature of the combustion chamber was higher than 800 degrees C, there was only a slight formation of PCDDs, PCDFs, and coplanar PCBs regardless of the chlorine content of the combustion samples. When the grate temperature was low, nearly 90% of total PCDDs, PCDFs, and coplanar PCBs formed were PCDFs, whereas when the grate temperature was higher, 50-80% of total PCDDs, PCDFs, and coplanar PCBs formed was PCDFs. The total amount of PCDDs, PCDFs, and coplanar PCBs formed in a high-temperature condition was approximately 1/50 of that formed in a low-temperature condition. Coplanar PCBs tended to form less than PCDDs or PCDFs did. Mono-ortho-PCBs were formed several times more than nonortho-PCBs. PCDDs or PCDFs contributed significantly to the values of TEQ, while coplanar PCBs contributed only slightly.     

Mechanistic relationships among PCDDs/Fs, PCNs, PAHs, CIPhs, and CIBzs in municipal waste incineration

An extensive investigation was conducted to understand polychlorinated dibenzo-p-dioxin and furan (PCDD/F) formation mechanisms and their relationship with other organic compounds. PCDD/F, chlorophenols (CIPhs), chlorobenzenes (CIBzs), polyaromatic hydrocarbons (PAHs), and polychlorinated naphthalenes (PCNs) were analyzed in the boiler exit gases of a field-scale municipal solid waste incinerator under various operating conditions. The TEQ value and the concentration of target compounds changed with incinerator operating conditions. Low mass PAHs and 246-triCIPh increased dramatically during shut downs; the latter was associated with increased 1368- and 1379-TeCDD. A strong correlation was observed between PCNs and PCDFs and adjacent PCNs homologue group were closely related to each other. This suggested that PCN formation is related with chlorination/dechlorination mechanisms similar to PCDFs. PCDDs were related with most of the CIPhs and the high chlorinated benzenes. Most of target compounds except PAHs had a positive correlation (R2 > 0.5) with TEQ and half of them showed a good relationship (R2 > 0.8) with PCDDs/Fs toxic equivalency (TEQ).     

Occurrence and destruction of PAHs,PCBs, CIPhs,CIBzs, and PCDD/Fs in ash from gasification of straw

Two experiments were performed with an atmospheric circulating fluidized bed gasifier (ACFBG), the first with pelletized straw and the second with loose straw, to investigate the occurrence of polycyclic aromatic hydrocarbons (PAHs), chlorophenols (CIPhs), polychlorinated biphenyls (PCBs), polychlorinated benzenes (ClBzs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) in the bottom ash and fly ash formed during gasification. Only PAHs were present in large amounts, and only in the fly ash, ranging from 300 to 555 mg/kg ash in the tests with pelletized straw and from 73 to 118 mg/kg ash in those with loose straw. These amounts are so high that environmentally safe disposal or reuse of the ash would be difficult, so the development of a technique to handle the problem was included in the project. The method investigated was to burn the fly ash in a circulating fluidized bed (CFB) boiler in order to destroy the PAHs. This worked surprisingly well, eliminating 99% of the PAHs, without any further formation of the other harmful organic compounds analyzed. Thus, this method could actually be useful in practice. Especially the fact that the formation of PCDD/Fs was minimal during gasification and further treatment of the ash in the CFB boiler makes the gasification technique highly competitive relative to conventional combustion methods.     

A Critical Review about Human Exposure to Polychlorinated Dibenzo-p-Dioxins (PCDDs), Polychlorinated Dibenzofurans (PCDFs) and Polychlorinated Biphenyls (PCBs) through Foods

Dioxins include polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and part of polychlorinated biphenyls (PCBs). Only the compounds that are chlorinated at the 2,3,7, and 8 positions have characteristic dioxin toxicity. PCDDs, PCDFs and PCBs accumulate in the food chain due to their high lipophilicity, high stability, and low vapor pressure. They are not metabolized easily; however their hydroxylated metabolites are detected in feces. They cause a wide range of endocrine disrupting effects in experimental animals, wildlife, and humans. Endocrine related effects of PCDDs, PCDFs and PCBs on thyroid hormones, neurodevelopment and reproductive development were referenced. In addition, some studies of contamination of foods, bioaccumulation, dietary exposure assessment, as well as challenges of scientific research in these compounds were reviewed.     

Effect of moisture, charge size, and chlorine concentration on PCDD/F emissions from simulated open burning of forest biomass

Loblolly pine (Pinus taeda) was combusted at different charge sizes, fuel moisture, and chlorine content to determine the effect on emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) as well as copollutants CO, PM, and total hydrocarbons. The experiments were performed in an enclosed chamber under conditions simulating open, prescribed burns of forest biomass. Burn progress was monitored through on line measurement of combustion gases and temperature while PCDD/F concentrations were determined by ambient sampling methods. PCDD/F toxic equivalency (TEQ) and total (tetra- to octa-CDD/F) emission factors were independent of charge size (1-10 kg) and moisture content (7-50%). However, the lower chlorinated, mono- to tri-CDD/F compounds were increased by poor combustion conditions: combustion efficiency lower than 0.919 was generally found when the moisture content was higher than 30%. The increase of fuel matrix chlorine from 0.04% to 0.8% using a brine bath resulted in about a 100-fold increase of PCDD/F to about 90 ng TEQ/kg of carbon burned, C(b). These emission factors were linearly dependent on Cl concentration in the biomass. PCDD 2,3,7,8-Cl-substituted congeners and homologue patterns were also influenced by the addition of chlorine resulting in emissions with a higher abundance of the most toxic congeners (TeCDD and PeCDD). When both chlorine and moisture content were increased in the fuel, a simultaneous effect of the two parameters was observed. The increased TEQ values expected from higher Cl concentrations were mitigated by the presence of water, giving MCE = 0.868, promoting formation of mono- to tri-PCDD/F, and lowering the TEQ value. Open burn simulations were used to study PCDD/F formation in different combustion conditions providing a mathematical correlation between PCDD/F emissions and chlorine and moisture content in the fuel.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and polychlorinated biphenyls in human tissues, meat, fish, and wildlife samples from India

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and non- and mono-ortho-substituted polychlorinated biphenyls (dioxin-like PCBs) were measured in tissues of humans, fishes, chicken, lamb, goat, predatory birds, and Ganges River dolphins collected from various locations in India. PCDDs/DFs were found in most of the samples analyzed with the liver of spotted owlet containing the highest concentration of 3,300 pg/g, fat wt. 2,3,7,8-Substituted PCDDs and PCDFs were found in human fattissues at concentrations ranging from 170 to 1,300 pg/g, fat wt. Concentrations of PCDDs were generally greaterthan those of PCDFs in human tissues, fishes, animal fat, and dolphin. Among fishes, meat, and wildlife samples analyzed, concentrations of PCDDs/DFs were found in the following order: country chicken < goat/lamb fat < fishes < river dolphins < predatory birds. Hepta-CDDs and OCDD were the major PCDD homologues found in humans, fishes, meat products, and dolphins. 2,3,7,8-Tetrachlorodibenzo-p-dioxin equivalents of PCDDs/DFs were greater than those of PCBs in selected fish, dolphin, and human samples. To our knowledge, this is the first report of PCDDs and PCDFs in human tissues, fishes, meat, and wildlife collected from India.     

Key parameters for de novo formation of polychlorinated dibenzo-p-dioxins and dibenzofurans

De novo formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs and PCDFs) was investigated in an Entrained Flow Reactor (EFR) to simulate combustion conditions. The parameters investigated were carbon content and nature in fly ash; type of gas-phase environment (oxidative versus reducing conditions) influence of combustion gases such as water, carbon monoxide, and carbon dioxide; amount of gas-phase chlorine; reaction temperature (250-600 degrees C); and reaction time (minutes vs hours). The comprehensive data set was further evaluated with principal component analysis (PCA) to statistically determine the role and importance of each parameter for de novo formation of PCDDs and PCDFs. Results revealed that an initial fast de novo formation occurs within the first minutes with a formation rate in the orders of hundreds of pmol per minutes; however, the reactivity of the ash was found to decline with time. An average formation rate as low as 3 pmol/min was measured after 6 h. The slower de novo formation of PCDDs and PCDFs was found to be through different reaction mechanisms and, thus, controlled by different parameters. The amount of Cl2 in the gas phase was observed to be an important parameter for PCDFs formation; meanwhile the levels of O2 were not found to be a PCDF rate controlling parameter. The formation rate of PCDDs was significantly lower than the PCDFs, and two mechanisms appear to be controlling the formation, one depending on the amount of O2 and one on the amount of Cl2 present in the gas phase. Overall the most significant parameter for the rate of formation for both PCDDs and PCDFs was revealed to be the reaction temperature. A maximum rate of formation was observed between 300-400 degrees C for the PCDDs and 400-500 degrees C for the PCDFs.     

Congener-specific distribution of polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in animal feed.

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were extracted by accelerated solvent extraction from animal feed samples and analysed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). In all of the feed samples analysed, the concentrations of PCDD/Fs and PCBs were below the existing tolerance limit of 5 pg I-TEQ g(-1) and 200 ng g(-1) fat, respectively. The mean concentrations of the total PCDDs, total PCDFs and total PCBs were 1.73-11.50 pg g(-1), 0.23-11.91 pg g(-1) and 60.00-234.40 pg g(-1) feed, respectively. Investigation of the correlations among the concentrations of PCDDs, PCDFs and PCBs showed that samples containing increased amounts of PCDFs also contained higher concentrations of PCDDs, with an average ratio of PCDF:PCDD of about 1.23:1 (r(2)=0.72, p<0.05). The correlation between the concentrations of PCDD/Fs and PCBs was positive but not significant.     

Formation of PCDD/Fs from the copper oxide-mediated pyrolysis and oxidation of 1,2-dichlorobenzene

Formation of polychorinated dibenzo-p-dioxins (PCDDs) has been demonstrated to occur via surface-mediated reactions of chlorinated phenols. However, polychlorinated dibenzofurans (PCDFs) are observed in much lower yields in laboratory studies than in full-scale combustors where PCDFs are in higher concentrations than PCDDs. This has led to the suggestion that at least PCDFs are formed from elemental carbon in the de novo process. However, the potential for PCDF formation from reactions of chlorinated benzenes has been largely overlooked. In this study, we investigated the potential contribution of chlorinated benzenes to formation of PCDD/Fs using 1,2-dichlorobenzene as a surrogate for reactions of other chlorinated benzenes and CuO/silica (3 wt % Cu) as a surrogate for fly ash. Results were similar for oxidative and pyrolytic conditions with a slight increase in more chlorinated products under oxidative conditions. Reaction products included chlorobenzene, polychlorinated benzenes, phenol, 2-monochlorophenol (2-MCP), dichlorophenols, and trichlorophenols with yields ranging from 0.01 to 2% for the phenols and from 0.01 to 10% for chlorinated benzenes. 4,6-Dichlorodibenzo furan (4,6-DCDF) and dibenzofuran (DF) were observed in maximum yields of 0.2% and 0.5%, respectively, under pyrolytic conditions and 0.1% and 0.3%, respectively, under oxidative conditions. In previous studies of the pyrolysis of 2-MCP under identical conditions, 4,6-DCDF and dibenzo-p-dioxin (DD) were observed with maximum yields of ～0.2% and ～0.1%, respectively, along with trace quantities of 1-monochlorodibenzo-p-dioxin (1-MCDD). Under oxidative conditions, 1-MCDD, DD, and 4,6-DCDF were observed with maximum yields of 0.3%, 0.07% and 0.1%, respectively. When combined with the fact that measured concentrations of chlorinated benzenes are 10-100× that of chlorinated phenols in full-scale combustion systems, the data suggest surface-mediated reactions of chlorinated benzenes can be a significant source of PCDD/F emissions.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in the air of Seveso,Italy, 26 years after the explosion

This study reports the current levels of polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in air at Seveso, where an explosion in a 2,4,5,-trichlorophenol production reactor occurred 26 years ago. The aims were to assess if residues of the 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) released during the accident and still present in soil could contaminate the above air and to investigate other potential sources in the area. Long-term air collection was carried out in zones A and B in Seveso and in a reference location in Milan, and samples were analyzed for PCDD and PCDF concentrations by gas chromatography-mass spectrometry (GC-MS). Experimental results showed that no important contribution to the air concentrations is due to the soil contamination and that contemporary sources essentially control the atmospheric burden of PCDDs and PCDFs in the Seveso area. The theoretical release of 2,3,7,8-TCDD from the soils of zones A and B of Seveso was calculated using the SoilFug model. In the worst case, the model simulated an enrichment in atmospheric 2,3,7,8-TCDD concentrations of 4 and 22% for zones A and B, respectively. The investigation of the potential emission sources in the area indicated that combustion of wood residues from furniture factories may be an additional local source of PCDDs and PCDFs.     

Role of chlorine in combustion field in formation of polychlorinated dibenzo-p-dioxins and dibenzofurans during waste incineration

Combustion experiments performed in the presence of hydrogen chloride (HCl) in a laboratory-scale fluidized-bed reactor were carried out to elucidate the role of chlorine in the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs; together: PCDD/Fs) in various sections of a municipal waste incinerator. We first demonstrated that the homologue profile and the pattern of the congener proportions of PCDD/Fs for a model waste containing poly(vinyl chloride) (PVC) combusted in the absence of HCl were similar to those for a PVC-free waste combusted in the presence of HCl. This showed no difference between PVC in the waste and injected HCl in the role as a chlorine source in PCDD/F formation during incineration. Next, to investigate PCDD/F formation in each section of the incinerator, we carried out combustion experiments with the PVC-free waste, injecting HCl at different locations of the incinerator. The amounts of PCDDs and PCDFs formed were significantly reduced when HCI was not supplied to the main combustion section. The presence of HCI in the main combustion section was essential for the formation of PCDD/Fs, even in the downstream sections. This finding indicates that compounds that were able to form PCDD/Fs in the downstream sections were mainly formed in the main combustion section in the presence of HCl.     

Organic carbon-water concentration quotients (II(SOC)S and pi(poc)S): measuring apparent chemical disequilibria and exploring the impact of black carbon in Lake Michigan

Chemical concentration quotients measured between water and total organic carbon (TOC) in sediment (II(SOC)) or suspended particulates (pi(poc)) in southern Lake Michigan reveal up to 2 orders of magnitude differences for polychlorinated biphenyl (PCB), dibenzo-p-dioxin (PCDD), dibenzofuran (PCDF), and polycyclic aromatic hydrocarbon (PAH) compounds with similar octanol-water partition coefficients (K(ow)S). Apparent disequilibria for PAHs, PCDDs, and PCDFs, determined as measured II(SOC)S or pi(poc)S divided by their organic carbon equilibrium partitioning values, are significantly greater than disequilibria of PCBs with similar K(ow)S. Apparent disequilibria, when adjusted for black carbon content by using published black carbon nonlinear partition coefficients (K(f,bc)S) and a Freundlich exponent (n(f)) value = 0.7, still exceed equilibrium predictions for the PAHs, PCBs, and PCDDs but with the PCDF disequilibria uniquely below equilibrium. While Monte Carlo analysis of all the variables associated with the black carbon adjusted disequilibria provides wide confidence intervals for individual chemicals, the large class disequilibria differences between PAHs and PCDFs with respect to the PCBs and PCDDs are highly significant. Use of the PCDD K(f,bc)S for calculating both the PCDF and PCDD disequilibria eliminates their extreme divergence. On the basis of the complexity of carbonaceous geosorbent effects and the apparent variable degrees of chemical sequestration in particles, the disequilibria can be adjusted by chemical class to meet expected near equilibrium conditions between suspended particles and water in the hypolimnion. Although these adjustments to the disequilibria calculations produce consistent and plausible values, the complexities of variable carbonaceous geosorbent affinities for these chemicals in Lake Michigan presently favor use of measured, rather than a priori modeled, steady-state total organic carbon-water concentration quotients indexed to TOC as biogenic organic carbon.     

Biota--sediment accumulation factors for polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans in southern Lake Michigan lake trout (Salvelinus namaycush)

A set of high-quality, age-specific biota-sediment accumulation factors (BSAFs) for polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) have been determined from concentrations measured with high-resolution gas chromatography/high-resolution mass spectrometry, by use of the 13C isotopic dilution technique, in lake trout and surficial (0-2 cm) sediment samples from southern Lake Michigan. BSAFs ranged from <0.1 to 18 for PCBs and from <0.001 to 0.32 for PCDDs and PCDFs detected in the fish. PCBs with zero or one chlorine in an ortho position had smaller BSAFs than other PCBs. PCDDs and PCDFs with chlorines at the 2,3,7,8-positions had larger BSAFs than most other PCDDs and PCDFs. The fidelity of the relative bioaccumulation potential data between independent lake trout samples, within and among age classes, suggests that differences in slight rates of net metabolism in the food chain are important and contribute to the apparent differences in BSAFs, not only for PCDDs and PCDFs but also possibly for some PCBs. A complicating factor for non-ortho- and mono-ortho-PCBs is the uncertain contribution of enhanced affinity for black carbon (and possibly volatility) acting in concert with metabolism to reduce measured BSAFs for lake trout. On the basis of the association between chemicals with apparent slight rates of metabolism and measured dioxin-like toxicity, several PCDFs with similar measured BSAFs but unknown toxicity may be candidates for toxicity testing.     

Approach to highly efficient dechlorination of PCDDs, PCDFs, and coplanar PCBs using metallic calcium in ethanol under atmospheric pressure at room temperature

Detoxification of highly toxic polychlorinated aromatic compounds such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like compounds such as coplanar polychlorinated biphenyls (co-PCBs) under mild conditions (atmospheric pressure and room temperature) was achieved by a simple stirring operation for 24 h using metallic calcium in ethanol, without any tedious decomposition procedures and harsh conditions such as high temperature and/or high pressure. Metallic calcium can be kept stable under atmospheric conditions for a long period as compared to metallic sodium since the surface is coated with CaCO3, which is formed in the contact with air. Moreover, ethanol, which is one of the safest solvents for humans, acts not only as a solvent but also as an accelerator due to its ablility to remove the carbonated coating. This decomposition method for PCDDs, PCDFs, and co-PCBs therefore is one of the most economical and environmentally friendly detoxification methods with respect to the input energy and safety of reagents used. Concentration for each isomer of PCDDs, PCDFs, and co-PCBs was reduced in 98.32-100% conversions by treatment in ethanol at room temperature. The toxicity equivalency quantity (TEQ), which was measured by the HRGC-HRMS analysis, for the total residues of isomers was reduced from 22,000 to 210 pg TEQ/mL of hexane (conversion: 99.05%) at room temperature. By refluxing over 24 h, the conversion increased up to 99.45%.     

纸浆漂白过程中二噁类的生成及控制

概述了纸浆漂白过程中二噁类的生成机理，介绍了减少二类生成量所应采取的措施。