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1.
Gullett BK  Wikström E 《Chemosphere》2000,40(9-11):1015-1019
Total homologue concentrations and select congener concentrations from amongst the mono- to tri-chlorinated dibenzodioxins (CDDs) and dibenzofurans (CDFs) are used to model both Total (mono- to octa-) CDD + CDF emissions and the toxicity equivalent (TEQ) of the 2,3,7,8-chlorine-substituted emissions. Analysis of emission data from two facilities indicates that use of total homologue concentrations shows limited, facility-specific correlations with Total CDDs/CDFs and TEQ. Concentrations of select mono- to tri-CDD/CDF congeners show promising correlation with CDD/CDF TEQ across facilities, suggesting that these compounds can act as TEQ indicators.  相似文献   

2.
V. Zitko 《Chemosphere》1985,14(2):165
Numbers in base 16 (Hex) are used for an abbreviated designation of chlorine substitution in CDD and CDF. This “shorthand” requires two hexadecimal digits. A letter (“d” or “f”) may be used to distinguish between CDD and CDF. The digits describe the substitution patterns in positions 6,7,8,9, and 4,3,2,1, assigned values of 8,4,2, and 1, respectively. For example, 66d = 2,3,7,8-tetrachlorodibenzo-p-dioxin.  相似文献   

3.
R.E. Clement 《Chemosphere》1986,15(9-12):1157-1164
A literature review of recent work involving the determination of chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF) in fish and incinerator samples has shown many irregularities and omissions in the reported data. Although some of these result from non-standardized nomenclature and reporting practices and do not affect the overall conclusions reached, in some cases omissions in reporting experimental procedures raise important concerns regarding the validity of data and make comparison of data from different investigations difficult. It is not always necessary or even desirable to report every experimental detail of work performed, however, the ultra-trace determination of CDDs and CDFs in complex environmental samples is still at a stage where omission of key experimental details can affect the interpretation of results.  相似文献   

4.
Several studies have found that current levels of 2,3,7,8 tetrachlorodibenzo-p-dioxin in serum lipids are related to age with older persons generally having higher levels. To account for this age pattern, reference ranges based on national samples have been established in order to allow determination of background levels for regional studies. In several studies, body mass index (BMI), has also been associated with current 2,3,7,8 tetrachlorodibenzo-p-dioxin levels with increasing body mass index related to increasing levels. We measured lipid-adjusted serum levels for all 2,3,7,8-substituted dioxins and furans in 62 chemical manufacturing workers with chlorophenol exposures and 36 workers without chlorophenol exposures employed at the same location. We then assessed the impact of age and BMI on the serum levels of all these compounds in the presence of other potential confounders. We found that both factors are important independent determinants of serum levels of 2,3,7,8-substituted dioxins and furans. Specifically, age and BMI are both important factors for assessing background levels of 2,3,7,8 tetrachlorodibenzo-p-dioxin, 1,2,3,7,8 pentachlorodibenzo-p-dioxin and the calculated total toxic equivalency. BMI, but not age, is important for assessing background levels of higher chlorinated dioxins and some hexachlorofurans. We conclude that age and BMI are both important considerations when comparing a potentially exposed group to a referent group, or to national norms. Further, age and BMI may also be important in epidemiology studies where back-extrapolation from current dioxin levels is used to assess historical chlorophenol exposure.  相似文献   

5.
Ryu JY  Choi KC  Mulholland JA 《Chemosphere》2006,65(9):1526-1536
Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.  相似文献   

6.
Ryu JY  Mulholland JA  Chu B 《Chemosphere》2003,51(10):1031-1039
Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O2 and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl2 and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl2 to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl2 was high, both in terms of CuCl2 utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl2 were observed between 200 and 300 °C; this suggests that nearly 100% CuCl2 was utilized, assuming a conversion of two moles of CuCl2 to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.  相似文献   


7.
Jon Knutzen

M. Oehme 《Chemosphere》1989,19(12):1897-1909

The contamination of a fjord region by PCDD and PCDF produced from a Mg-production plant has been studied. Levels in organisms (fish, crustacea, mussels) and sediments were determined. The results allowed an estimate of the spreading of PCDD/PCDF by coastal currents. The present situation is compared with available information from other contaminated areas and with data for other contaminants in the recipient area such as hexachlorobenzene and octachlorostyrene.  相似文献   

8.
The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl2), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl2 occurred as a result of a metal-catalyzed reaction of HCl with O2. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.  相似文献   

9.
R.E. Clement  B. Bobbie  V. Taguchi 《Chemosphere》1986,15(9-12):1147-1156
A study was designed to determine the feasibility of using GC-MS-MS techniques for the determination of chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF) in difficult environmental samples with reduced cleanup. Three fish and three sediment extracts were provided to six different laboratories with GC-MS-MS capability for analysis. In addition, extracts were analysed by GC-low reduction MS (LRMS) and GC-high resolution MS (HRMS). At the time of this report, all participating GC-MS-MS laboratories had not completed their analysis of the supplied samples. All reporting laboratories found the analysis of these very complex samples difficult without extensive cleanup. GC-HRMS determination of some samples was possible with reduced cleanup compared to GC-LRMS.  相似文献   

10.
Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM10) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m−3 to 52 fg WHO-TEQ m−3 in particulate fraction. The PM10 concentrations ranged from 23 μg m−3 to 54 μg m−3. Concentrations of PM10 and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM10 found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical Kp data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM10 (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM10. Poor correlation between precipitation and reduced PM10 concentration in ambient air (r = −0.45) suggested low PM10 removal by rainfall.  相似文献   

11.
An analytical procedure has been developed for quantitatively measuring dibenzo-p-dioxin (DBD) and dibenzofuran (DBF) present at part-per-billion levels in paper mill defoamers and paper pulp using gas chromatography coupled with either low resolution mass spectrometry (GC-LRMS) or high resolution mass spectrometry (GC-HRMS).  相似文献   

12.
Expanded, 45 reaction, and core, 12 reaction, kinetic models have been developed that account for the major features in the homogeneous formation of polychlorinated dibenzo-p-dioxins (PCDD) from the oxidation of 2,4,6-trichlorophenol (P). The expanded and core schemes provide good agreement between experimental and calculated yields of PCDDs using the CHEMKIN combustion package or the React kinetic program, respectively. Steady-state approximations of the reaction kinetic models including radical-molecule and radical-radical formation pathways of PCDD, as well as oxidative destruction pathways of chlorinated phenoxyl radicals, reveal a competition between reactions of chlorinated phenoxyl radicals with chlorinated phenols, recombination reactions of chlorinated phenoxyl mesomers, and destruction/decomposition of phenoxyl radicals.  相似文献   

13.
The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid–liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25–25 µg L?1 of 1.25–20 µg L?1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.  相似文献   

14.
The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m3 sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm3. In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.  相似文献   

15.
Although 2,3,7,8-TCDD has been found to be extremely toxic to a variety of laboratory aminals, human epidemiology studies, where exposure to 2,3,7,8-TCDD has been less well characterized than in animal toxicologic studies, have been less conclusive in characterizing the extent of toxicity. In order to determine whether the newly refined techniques of human adipose tissue biopsy including isomer specific and sensitive measurement of PCDDs and PCDFs might be able to assist in finding populations within the same country with high and low levels of dioxins, adipose tissue samples were taken and levels analyzed from the north and south of Vietnam. It seemed reasonable, based on previous work, that high levels of 2,3,7,8-TCDD might still be found in adipose tissue in selected patients living in areas sprayed with Agent Orange and other 2,3,7,8-TCDD containing herbicides, and that lower levels should be found in patients not exposed to 2,3,7,8-TCDD from herbicides or other sources, such as persons who had always resided in the north of Vietnam. Of 9 specimens from patients hospitalized in Hanoi who had never been south, none had detectable adipose tissue levels of 2,3,7,8-TCDD at a detection limit of 2 or 3 ppt on a wet weight basis. Of 15 specimens from Ho Chi Minh City hospitalized patients the mean of positive specimens (12 of 15) was 28 on a lipid basis. The mean of the positive values from the south is about 2 to 3 times higher than found in the North American Continent control patients where the mean is about 6–10 ppt and much higher than in the north of Vietnam. In the northern specimens, the levels were non-detectable with a sensitivity of between 2 and 3 ppt. Other PCDD and PCDF isomers not found in Agent Orange, the penta- through octachlorinated dibenzo-dioxins and dibenzofurans, were similar in isomer type and quantity in the south of Vietnam to what we previously reported in North America. Adipose tissue from the north of Vietnam contained the lowest levels of four through eight chlorinated dioxins and furans thus far reported. The initial data suggests that populations exist in the south of Vietnam with elevated levels of 2,3,7,8-TCDD at the present time, fourteen years after the last known 2,3,7,8-TCDD (Agent Orange) application, superimposed on a preexisting body burden of dioxins and dibenzofurans from sources other than Agent Orange such as technical grade pentachlorophenol or products of incineration contaminated with higher chlorinated PCDDs or PCDFs. In light of the recent finding that unexpected levels of PCDDs and PCDFs exist in the general adult population of industrialized countries, ca. 1,000 to 1,200 ppt, wet weight of total dioxin and furan isomers in adipose tissues, it seems reasonable that the extent of human toxicity of dioxins may be more readily characterized in Vietnam than in industrialized countries. Because 2,3,7,8-TCDD was applied in 1962–1970, although not yet cleaned up, the levels of 2,3,7,8-TCDD in the environment, the food chain, and in humans, would be expected to decrease with time. Therefore, if studies are not initiated in a timely fashion, the opportunity to better characterize the extent of the toxicity of TCDD to humans as well as the persistence of TCDD in the environment in Vietnam may be lost.  相似文献   

16.
The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.  相似文献   

17.
Ryu JY 《Chemosphere》2008,71(6):1100-1109
Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.  相似文献   

18.
D. Thompson 《Chemosphere》1994,29(12):2583-2595
A database for chlorinated dioxins (DBDs), with heats of formation derived by analogy with chlorination of quinone and benzene, has already been shown to predict relative isomer distributions nearer to those observed, and those predicted using MOPAC, than an earlier database due to Shaub. The model has been extended to obtain a similar database for chlorinated dibenzofurans (DBF's), and comparisons with observed isomer concentration distributions are illustrated. Calculations are carried out using the NPL MTDATA suite of programs. Isomer group values for the properties of the original compounds and each degree of chlorination have been derived, and the use of these values leads to a reduction in the data obtained in computations to more manageable proportions. The reduced database obtained is combined with other databases to carry out computer predictions for simulated chlorine-containing combustion gases. Data for inorganics substances and the simplest organic substances (methane. ethane and related species) are obtained from the SGTE database. More extensive data for aliphatic and aromatic hydrocarbons from various standard sources have been incorporated in an additional computational database. In order to examine the relative concentrations of DBFs and DBDs a database for chlorinated hydrocarbons has been established. Predictions for simulated fuel rich combustion products for the C, H, O, Cl system are presented.  相似文献   

19.
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 TEQPCDD/F+dioxin-like[DL]-PCB g−1 lipid to 12.8 pg TEQPCDD/F+DL-PCB g−1 lipid (median 0.342 pg TEQPCDD/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 TEQPCDD/F+DL-PCB g−1 lipid) exceeded the European toxic equivalent concentration limits for eggs (5 pg TEQPCDD/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.  相似文献   

20.
Zhang J  Zhou J  Jiang Y  Jiang J  Zhuang Z  Liu X  Wu Y 《Chemosphere》2007,66(2):199-202
Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) concentrations in 31 fish samples from 19 commonly consumed freshwater and saltwater species from the Pearl River Delta Area were analyzed. The PCDD/Fs dietary intake from fish for the local population was evaluated to provide a database for setting the national PCDD/F limits in fish for the People's Republic of China. The median concentration from the 31 fish samples was 1.27 pg/g wet weight for the total of PCDD/Fs, and the median WHO-TEQ was 0.26 pg/g wet weight, and ranged from 0.063 to 1.30 pg WHO-TEQ/g wet weight. The dominant contributors to the WHO-TEQ were 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF, which accounted for 38% and 28%, respectively. The dietary intake of PCDD/Fs from fish for local people was estimated to be 0.47 pg WHO-TEQ/kg bw x day. In view of the findings, the dietary of PCDD/Fs from other foods of animal origins in China should be studied in more detail as soon as possible in order that standards can be put forward to protect human health.  相似文献   

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