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1.
Eight sewage sludges from rural, urban and industrial wastewater treatment plants (WWTPs) in Catalonia (Spain) were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) to determine the present levels of contamination. A method based on an automated cleanup system followed by an isotope-dilution high-resolution mass spectrometric analysis was employed. Total toxicity equivalent (WHO-TEQ) values were calculated using the toxicity equivalent factors (WHO-TEFs) proposed by WHO for dioxin-like PCBs, PCDDs and PCDFs. The WHO-TEQ(PCDD/F) values for these samples ranged from 4.9 to 20.8 pg/g dry weight (d.w.), with a mean value of 9.3 pg/g d.w., whereas WHO-TEQ(PCB) levels ranged between 1.9 and 6.6 pg/g d.w., with a mean value of 4.2 pg/g d.w. The WHO-TEQ(PCB) contribution varied from 13% to 50%, suggesting that PCB contribution on the toxicity of the samples must be taken into account. Moreover, these contemporary PCDD, PCDF and PCB concentrations were compared with previous data obtained from sewage sludge samples collected during the 80s. Our findings show that contemporary PCDD, PCDF and PCB levels have declined since the 80s.  相似文献   

2.
PCDD/PCDF,chlorinated pesticides and PAH in Chinese teas   总被引:5,自引:0,他引:5  
Fiedler H  Cheung CK  Wong MH 《Chemosphere》2002,46(9-10):1429-1433
Four samples of Chinese tea (two green teas, and two brick teas) were analyzed for their concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF), chlorinated pesticides and PAH. The infusions prepared from these teas were also analyzed for PCDD/PCDF. The levels of DDT and its metabolites in tea leaves were within the safety limit of 0.2 mg/kg. Rather high levels of total PAH were obtained in brick tea (1048–1162 mg/kg), when compared with green tea (497–517 mg/kg). In terms of PCDD/PCDF, the concentrations of green tea and brick tea differed by a factor of 16, while the concentrations of all infusions were within a factor of 2. The dioxin concentrations in green tea leaves can be explained through uptake of atmospheric PCDD/PCDF. The higher concentrations in the brick tea leaves are due the longer exposure time, and to certain extent, the use of old leaves, branches and roots when making the tea, and additional components such as soil particulates through contamination. Certain Chinese populations drinking a large amount of brick tea (>3 l per day) indicated that individuals of these populations consume more tea than Europeans or North Americans result in a comparably higher intake of PCDD/PCDF. Tea consumption can attribute to up to 10% of the TDI recommended by WHO (only PCDD/PCDF considered, no PCB analyzed).  相似文献   

3.
Seepage water of toxic waste landfills is polluted with high concentrations of toxic organic compounds. The concentrations in the seepage water we applied for chlorinated phenols are between 2 μg/1 and 1 mg/l, for PCB between 800 pg/l and 250 ng/l, for PAH between 200 ng/l and 12 μg/l and for PCDD and PCDF between 20 pg/l and 1 ng/l. Usual purification methods produce highly contaminated residues, which have to be treated by pyrolysis or are deposited again at a landfill. A better way is to destruct these contaminants by UV/ozone treatment. The treatment of seepage water by UV-irradiation, ozone and UV/ozone is compared. Results show no significant effect during all treatments for PCB and PCDD/PCDF. The chlorinated phenols and PAH were mostly destroyed by UV/ozone treatment more than 90 %. The pH value has no influence on the UV/ozone treatment of seepage water.  相似文献   

4.
Dated sediment cores provide an excellent way to investigate the historical input of persistent organic pollutants into the environment and to identify possible sources of pollution. The vertical distribution of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyls (PCB) was investigated in a sediment core from Greifensee to elucidate the historical trends of PCDD/F and PCB inputs between 1848 and 1999. Concentrations of PCB and PCDD/F increased by more than one order of magnitude between 1930 and 1960. PCB and PCDD/F concentrations were 5700 ng/kg dry weight (dw) and 160 ng/kg dw, respectively, in sediments originating from the late 1930s and reached a maximum of 130,000 ng/kg dw and 2400 ng/kg dw, respectively, in the early 1960s. From 1960 on, concentrations decreased to the 1930s level by the mid 1980s. A remarkable shift in the PCDD/F pattern was observed after the early 1940s. Before 1940, the PCDD/F pattern was PCDF dominated (ratio of PCDD to PCDF=0.41+/-0.11), while the PCDD started to be the major species after the early 1940s (ratio of PCDD to PCDF=1.46+/-0.38). The temporal trends of PCB and PCDD/F correlate surprisingly well with each other. This might be due to the coincidence of two factors. The introduction of PCB on the market in the 1930s resulted in emissions due to the widespread use of these industrial chemicals. In the same time period, waste incineration became an increasingly popular way to get rid of garbage, boosting the PCDD/F emissions significantly. The rapid decline of PCDD/F and PCB concentrations in the sediment starting in the early 1960s reflects the result of better emission control techniques in thermal processes and the improvement of waste water treatment in the catchment of Greifensee.  相似文献   

5.
In Germany, there is a lack of consistent and comparable data for the time dependent behaviour and spatial distribution of dioxin-like and indicator PCB in ambient air, deposition and plants. The aim of this study was to improve the data on PCDD/PCDF, dioxin-like PCB and non dioxin-like PCB in spruce and pine shoots from different locations and years by retrospective monitoring. The survey was conducted with archived samples of one-year old spruce shoots (Picea abies) and pine shoots (Pinus sylvestris) from the German environmental specimen bank. Two sets of samples from locations in urbanized areas in western and eastern Germany (Warndt and Duebener Heide Mitte, respectively) were investigated as time series. Additionally, spruce shoots from seven different rural locations sampled in the years 2000-2004 were analyzed in order to get an overview about the spatial distribution of PCB and PCDD/PCDF. The analytical results of the samples from the two urbanized areas clearly show that the atmospheric contamination with PCDD and PCDF has declined by about 75% between 1985 and 1997 at Warndt and about 40% between 1991 and 1997 at Duebener Heide. However, concentrations stayed virtually constant at both locations from 1997 to 2004 at a level of about 1 ng WHO-TEQ/kg dry matter (d.m.). Similarly, the investigation of spruce shoots from rural locations from 2000 to 2004 did not reveal a temporal trend at any site. PCDD/PCDF levels were between 0.1 and 1.0 ng WHO-TEQ/kg d.m. At the urbanized location Warndt the six indicator PCB as well as the 12 dioxin-like PCB according to WHO revealed a significant decline by more than 75% between 1985 and 1999. Thereafter, PCB levels stayed virtually constant. At the location Duebener Heide an overall decrease of PCB concentrations in pine shoots of about 60% was detected between 1991 and 2004. Spruce shoots from all locations showed a relevant contribution of dioxin-like PCB to the total WHO toxicity equivalent (PCDD/PCDF+PCB). In most samples, the contribution of dioxin-like PCB was between 21% and 41%. The TEQ contribution of PCB in the samples from three rural sites was higher and similar to the TEQ value of PCDD/PCDF. The investigated pine shoots from the urbanized site Duebener Heide showed a 15-28% contribution of dioxin-like PCB to total TEQ and thus lower than in spruce shoots from different locations. In all samples except one PCB 126 contributed to more than 80% to the PCB-TEQ.  相似文献   

6.
C. Cuiu  R. Halman  K. Li  R.S. Thomas  R.C. Lao 《Chemosphere》1986,15(9-12):1091-1098
Sample extracts from each section of a blank stack sampling train are portioned into two fractions, one to be used for PCDD/PCDF and PCB/CB analysis and the other for PAH/CP. The results of recovery studies for spiked compounds are presented. Developed protocols will be applied to future stack sampling programs and other environmental monitorings.  相似文献   

7.
Eighteen teachers from a highly contaminated school and 11 teachers from a control school participated in this study. Total polychlorinated biphenyl (PCB) indoor air concentration (six indicator congeners x 5) was beyond 12000 ng/m3 in some rooms of the contaminated school. PCB 28 and PCB 52 were the prevailing congeners. Whole blood was taken from each participant by the local health authority, pooled in two groups and analysed for the six PCB indicator congeners, non-ortho PCBs and polychlorinated dibenzodioxins (PCDD)/polychlorinated dibenzofurans (PCDF). Blood analysis showed elevated mean PCB 28 and PCB 52 levels for the exposed group, however the two groups were almost identical with regard to PCB 101, 138, 153 and 180. Moreover no difference can be observed for the concentration of non-ortho PCBs and PCDD/PCDF. The data support the finding, that heavy indoor air contamination with low chlorinated PCBs causes an increase of PCB 28 and PCB 52 blood levels. However, this increment was small compared to their total PCB load.  相似文献   

8.
The difference of polychlorinated dibenzofurans (PCDF) isomer patterns between stoker type incinerators and some fluidized bed incinerators (FBI) is a key to understand the formation mechanisms in both types of incinerators. The total yield and the isomer patterns of PCDF, polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), and polychlorinated benzenes (PCBz) formed via de novo synthesis from polycyclic aromatic hydrocarbons (PAH) indicate that chlorinated aromatics in the FBI are formed as a result of PAH breakdown. The detailed analysis of the isomer patterns of PCDF, PCB and PCN gives a first insight into the transformation mechanism of the PAHs and the sequence of degradation, chlorination and oxygen insertion. The major chlorination takes part at the position of the C-C cleavage during degradation of the PAHs. Further chlorination of the hydrogen position of the former PAH takes part preferably in ortho-position to this chlorination or is directed by incorporated oxygen. A perylene structure in soot is proposed as basis for the observed PCDF pattern in the FBI. Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated phenols (PxCP) were formed in lower concentrations from the de novo experiments indicating an additional formation pathway for these compounds in the FBI.  相似文献   

9.
Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1–3 pg/g−1 fat (0.2–1.6 pg ml−1 milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.  相似文献   

10.
Open burning for waste disposal is, in many countries, the dominant source of polychlorinated dibenzodioxins, dibenzofurans and biphenyls (PCDD/PCDF/PCB) release to the environment. To generate emission factors for open burning, experimental pile burns of about 100 kg of household waste were conducted with emissions sampling. From these experiments and others conducted by the same authors it is found that less compaction of waste or active mixing during the fire - “stirring” - promotes better combustion (as evidenced by lower CO/CO2 ratio) and reduces emissions of PCDD/PCDF/PCB; an intuitive but previously undemonstrated result. These experiments also support previous results suggesting PCDD/PCDF/PCB generation in open burning - while still highly variable - tends to be greater in the later (smoldering) phases of burning when the CO/CO2 ratio increases.  相似文献   

11.
The emissions from deep-seated fires in domestic waste have been investigated. The gas phase yields of PAH, PCDD/F, PCB, HCB, particles, and metals associated to the particulate matter were analysed during a series of simulated deep-seated fires. The method of extinguishment was varied and in cases where water was used for extinguishment, the runoff water was analysed for PAH, PCDD/F, PCB, hexachlorobenzene, and metals. In total six tests were performed. In four of the tests, samples of the fire residue were analysed for PCDD/F, PCBs, and chlorobenzenes.  相似文献   

12.
Sediment cores taken from the deep basin of Loch Coire nan Arr in north-west Scotland were dated using 210Pb calibrated spheroidal carbonaceous particle (SCP) profiles and analysed for trace metals, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). These data show that the site is one of the least contaminated by atmospheric pollution in the UK. Peak concentrations of PAHs were found to be equivalent to background values at sites in the English Lake District. The date of concentration maxima for SCP, PCB and some metals were in agreement with previously published polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran (PCDD/F) data suggesting long-range industrial sources. The date of individual PAH concentration maxima were earlier, but concomitant with each other, possibly suggesting the influence of a local source. Comparison with remote European mountain lakes shows Loch Coire nan Arr to be one of the least contaminated sites in Europe with respect to PCBs, but more contaminated with respect to PAHs.  相似文献   

13.
Cunliffe AM  Williams PT 《Chemosphere》2006,62(11):1846-1855
The development of an analytical method for the analysis of PCDD/PCDF in flyash using a bench analytical system comprising of a gas chromatograph fitted with an ion trap detector operated in the tandem MS mode is described. The optimum settings for the most important MS/MS parameters are given, including those for the less reported mono- to tri-chlorinated dioxin and furan congener groups. Flyash samples from three waste incineration plants representing a decommissioned 1970s plant design, an upgraded and still operating plant originally designed in the 1970s, and a modern 1990s design operating plant have been analysed for PCDD/PCDF. The flyash samples were analysed for PCDD/PCDF using the methods developed and the total PCDD/PCDF, I-TEQ values and isomeric profiles are reported. The flyash from the older decommissioned incinerator had very significantly higher concentrations of PCDD/PCDF compared to the modern incinerator flyash.  相似文献   

14.
Wobst M  Wichmann H  Bahadir M 《Chemosphere》2003,51(2):109-115
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.  相似文献   

15.
Despite their environmental importance, there are still relatively few historical studies of the environmental occurrence of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), especially in middle Europe. Trends in PCBs and PCDD/Fs were, therefore, assessed in lake sediments of the Grosser Arbersee over the past 130 years (1860-1990). Ballschmiter-PCB concentrations (congeners # 28, 52, 101, 138, 153, 180) increased between 1946 and 1972 from 4.2 to 32.0 microg kg(-1) dry wt, but have since decreased to 25.6 microg kg(-1) dry wt. High chlorinated PCB congeners reached their maxima earlier (1968-1972) than low chlorinated congeners (1985-1991). These trends were consistent with patterns expected from the production and use of PCBs and their precursors. PCDD/F concentrations increased between 1950 from 0.6 microg kg(-1) dry wt to 2.3 microg kg(-1) dry wt in 1977, falling to 1.7 microg kg(-1) dry wt by 1993. PCDF concentrations exceeded those of PCDD until 1968, but afterwards PCDDs (especially OCDD) were predominant. These patterns suggest that domestic heating and waste combustion were the most likely sources, but pollution from local industries, such as metal smelting and glass production, might also have been involved. The data provide a valuable case study from central Europe which confirms the overall declining trends of PCB and PCDD/F contamination shown elsewhere.  相似文献   

16.
Experiments at a pilot scale waste incinerator (0.5 MW thermal power) showed that the conditions in the post-combustion chamber (650-900 degrees C) are strongly influencing the formation of chlorinated and non-chlorinated aromatics. Non-optimal combustion conditions resulted in increased concentrations of mono- to trichlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and polycyclic aromatic hydrocarbons (PAH), while chlorinated benzenes (PCBz), polychlorinated biphenyls (PCB) and the higher chlorinated PCDD/F are only weakly affected or even decrease. The changes in concentration of the compounds investigated over a time span of hours gave hints on 'memory effects' in this combustion zone. For mono- and dichlorinated benzenes, a high correlation (r2 = 0.80) with the international toxicity equivalent (I-TEQ) value of PCDD/F was observed. As recently has been demonstrated, this correlation can be utilized for an indirect on-line measurement of the I-TEQ by a novel laser mass spectrometric technique (REMPI-TO-FMS).  相似文献   

17.
The aim of this study was to determine a new spectrum of substances that will be selected for future breast milk monitoring in Bavaria, Germany. Up to now, the analysis of breast milk in Bavaria was limited to selected organochlorine pesticides (OCP) and polychlorinated biphenyls (PCB). Information on background levels of toxicologically interesting substances, such as dioxins and dioxin-like polychlorinated biphenyls (dl-PCB) or on flame retardants, such as polybrominated diphenyl ethers (PBDE) are very limited or not available for Bavaria. We present here levels on OCP, some nitro musks, indicator PCB, polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and dl-PCB concentrations in breast milk collected at 12 weeks post-partum of 43 primiparous mothers living in Bavaria. The average concentrations of PCDD, PCDF and dl-PCB were 4.98, 4.93 and 9.92 pg WHO-TEQ g(-1) lipid, respectively. The mean contribution of PCDD, PCDF, non-ortho and mono-ortho PCB to the total WHO-TEQ is consistently about 25% each. Furthermore the concentration on PBDE in breast milk at two sampling points, 12 weeks and 16 weeks after delivery, were determined. Overall, 19 PBDE congeners were analysed, however the level of 12 PBDE congeners were below the limit of detection. BDE-153 and BDE-47 were the predominant congeners accounting for about 66% of the total PBDE. The means of the total concentrations of PBDE (five congeners) at the first and second sampling point were 1.90 and 2.03 ng g(-1) lipid, respectively. Based on our results the overall concentrations of the analysed substances in milk samples from Bavaria are consistent with the levels of breast milk samples of other European countries reflecting the low background body burden of these compounds.  相似文献   

18.
In 2003, concentrations of altogether 17 PCDD/Fs congeners and 12 non-ortho and mono-ortho dioxin-like PCBs were measured in the blood of 60 randomly selected adults who lived in three settlements surrounding a chemical plant that had been producing chlorinated herbicides (mainly HCHs, HCB, pentachlorophenole, 2,4,5-T) in the 1960's; subjects consuming home-produced animal foods were chosen. Twenty blood donors with similar characteristics from the locality with about 80 km distance were used as control subjects. The factors that influenced the dioxin levels were investigated on the basis of a questionnaire. The aim of our study was to find out whether the residents living in the surroundings of the chemical plant are at a greater exposure risk than the controls. To calculate TEQ values, WHO-TEFs were used. The concentrations of four PCDD and six PCDF congeners were below the LOD in more than 50% of samples. Significantly higher WHO-TEQ levels (p<0.05) were found for PCDDs, PCDFs, or PCBs in all three followed up groups compared with controls. The geometric means of the total TEQ values for PCDD/F/PCBs were 43.8, 50.2, and 40.0 pg/g fat compared to 23.2 pg/g fat in the control. The percentages of TEQ due to the measured congeners in exposed groups were 9-10.3% for PCDDs, 20.5-26.9% for PCDFs, 19.2-23.1% for coplanar and 43.6-47.2% for mono-ortho PCBs. In control, the percentage of TEQ was 11.6, 26.7, 24.1, and 37.5%. PCBs, predominantly PCB156, followed by PCB126 contributed 60 to 70% of the total TEQ value. Positive correlation of the PCDD/PCDF/PCB blood levels with age and with consumption of locally produced eggs was found.  相似文献   

19.
Baltic herring samples caught from the Baltic Sea during the spring periods of 1993-1994 and 1999 were analysed for polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF), and polychlorinated biphenyls (PCB). For analyses, 1570 individual herring were combined to 120 pools. Correlations between concentrations of congeners 1,2,3,7,8-PeCDD, 1,2,3,7,8-PeCDF, 2,3,4,7,8-PeCDF, and 2,3,4,6,7,8-HxCDF, and age of herring were the strongest (r>0.8) followed by correlations between PCB congeners PCB 105, 118, 126, 156, 169 and 180 (r>0.7), and age of herring. Due to higher fat percentage in herring in the Gulf of Bothnia the concentrations of PCDD/Fs and PCBs on fresh weight (fw) basis were higher than in herring in the Gulf of Finland. The concentrations of WHO(PCDD/F)-TEQs ranged from 1 to 27 pg/g fw, depending on the age and catchment area of herring, and concentrations of WHO(PCB)-TEQs reached 32 pg/g fw. Between the two studied time points no clear downward trend in concentrations was observed.  相似文献   

20.
Chi KH  Chang MB  Kao SJ 《Chemosphere》2007,68(9):1733-1740
Polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF) and polychlorinated biphenyl (PCB) concentrations were analyzed at 1-2cm intervals in a sediment core collected from a reservoir in Northern Taiwan to evaluate the organic pollution history. The highest PCDD/F (14.4ng TEQ/kg d.w.) and PCB (0.261ng TEQ(WHO)/kg d.w.) concentrations were determined at 13-15cm (estimated year: 1992). The ages of the levels of sediment core were estimated from the sedimentation rate. Analysis results demonstrate that the PCDD/F concentration of the sediment core measured in the reservoir reached their peak when the municipal waste incinerators (MWIs) in the area started to operate. Furthermore, the decrease in sediment core PCDD/F concentration is related to the time of enforcement of the PCDD/F emission limit set by the Environmental Protection Administration (EPA) in Taiwan. Significant distribution of OCDD in homologue profiles was noted in archived soil samples in Taiwan in which the major input of PCDD/Fs was thought to be atmospheric. Major PCB congeners found in the sediment core were the major components of the commercial PCB products. Input fluxes of PCDD/Fs (5.75-158ng-I-TEQ/m(2)-yr) and PCBs (0.248-3.71ng TEQ(WHO)/m(2)yr) into the reservoir of interest are also calculated from the concentration and sedimentation rate of the sediment. The results reveal that considerable amounts of PCDD/Fs and PCBs were carried into the reservoir of interest in the flood stage but not during normal stage.  相似文献   

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