Congener-specific accumulation of polychlorinated biphenyls in ovarian follicular wall follows repeated exposure to PCB 126 and PCB 153. Comparison of tissue levels of PCB and biological changes

OBJECTIVE: Small (SF), medium (MF) and large (LF) preovulatory porcine follicles were isolated and incubated in an Erlenmeyer flask containing 5 ml of medium with addition of PCB 126 or PCB 153 to test differences in their accumulation in the follicular wall. METHODS; The follicles were incubated in M199 medium at 37 degrees C with constant shaking at 70 rpm, for 6 days. The media were changed every day and repeated dose 25 pg/ml of PCB 126 or 25 ng/ml of PCB 153 was added each day till 6 days of culture. Media were collected every day and frozen for steroid analysis by RIA. 24 h after the last treatment follicles were frozen for further polychlorinated biphenyls (PCB) content analysis. PCB concentrations in the follicular wall were analysed by mass spectrometry. RESULTS: 3.3%; 3.6% and 5.6% of total PCB 126 dose, and 71%; 71.4% and 30.4% of total PCB 153 dose accumulated in SF, MF and LF follicles, respectively. The accumulative effect of PCB was manifested by the disruption of estradiol (E2) secretion. In SF antiestrogenic action of PCB 126 was observed during the whole time of exposure while PCB 153 decreased E2 till 4 days of culture and then estrogenic action was observed. In MF, both these congeners decreased E2 till 5 days of exposure and then estrogenic actions were noted with the highest magnification in the case of PCB 126. In LF both PCB studied increased E2 till 3 days of exposure with the highest magnification of PCB 126, then antiestrogenic action was noted. Testosterone secretion was generally affected in a pattern oposite to that of E2 suggesting action on P450arom activity. CONCLUSION: The results of these studies demonstrated that disruption of aromatization process in the follicles following repeated exposure to both congeners is not directly correlated with the bioaccumulation or amount of PCB within the follicular wall.     

Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

The variability of PCDD/F concentrations in the effluent of wastewater treatment plants with regard to their hydrological environment

The occurrence, concentrations, patterns, and loads of 17 2,3,7,8-substituted congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in treated wastewater collected at the outlets from 14 wastewater treatment plants (WTPs), divided into three size categories. The analysis also considered the effect of wastewater outflow on the final concentrations of PCDDs/Fs, as the samples were collected during flooding and stable hydrological conditions. None of the studied WTPs were found to completely remove toxic congeners of PCDDs/Fs from wastewater: the PCDD concentrations in the outgoing effluent during stable wastewater flow ranged from 2.99 to 177.19 pg/L, PCDFs from 6.05 to 51.30 pg/L, and the Toxic Equivalent (TEQ) was between 0.94 and 4.87 pg/L. The results from high wastewater flow were less diversified, ranging from 5.04 to 8.85 pg/L for PCDDs, from 11.47 to 32.33 pg/L for PCDFs and from 2.00 to 4.65 pg/L for TEQ. The smallest WTPs demonstrated the highest average total and TEQ concentrations due to limited volume, short retention time and outdated technology, and, hence, insufficient treatment efficiency. The largest WTPs have the potential to substantially affect the quality of river water, as despite being associated with the lowest concentrations, they released much greater volumes of treated wastewater and, hence, the greatest amounts of analyzed compounds. Elevated TEQ values were observed at high flow in all WTP size categories indicating the impact of high and stable wastewater flow on the concentrations of the observed PCDDs/Fs.     

PCDDs/PCDFs, dl-PCBs and HCB in the flue gas from coal fired CFB boilers

The aim of the project was to measure the actual emissions of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and hexachlorobenzene (HCB) from four selected power plants in Poland in order to update the national inventory of PCDDs/PCDFs emission. Relatively low PCDDs/PCDFs as well as dl-PCBs concentrations in flue gas obtained in measurements in this study for four different circulated fluidized bed (CFB) boilers indicate practical absence of any hazards caused by PCDDs/PCDFs emission from these units. The results of PCDDs/PCDFs determination obtained in this study indicate that hard coal combustion in large CFB in the four central heating plants (CHP) is not a significant source of PCDDs/PCDFs emission to the environment even if operated by co-firing of waste coal. PCDDs/PCDFs concentration in flue gases as well as emission factors were recorded in the range of 0.012-0.060ngI-TEQ/m(n)(3) and 7.51-46.4mugI-TEQ/TJ, respectively. Dl-PCBs concentration was practically below the LOQ=0.006ng WHO-PCB TEQ/m(n)(3) in all experiments. HCB concentration as well as emission factors were recorded in the range of 11.5-42.0ng/m(n)(3) and 6.19-26.7mg/TJ, respectively, where the highest value was obtained for co-firing of waste coal, however. Obtained in this work emission factors will be used for national emission inventory purposes instead of the factors proposed by Toolkit or taken from previous measurements. However, consideration should be given to the fact that the measurements in most cases are related to single installations. Therefore, the need for further development of national factors for the power generation industry in Poland is desired.     

Survey of dioxin sources in the Baltic Region (extended summary)

The present paper summarises the results of the project: 'Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region'. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88-1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.     

Estrogenic and antiestrogenic effect of in vitro treatment of follicular cells with 2,3,7,8-tetrachlorodibenzo-p-dioxin

OBJECTIVE: Two types of follicular cells from preovulatory ovary were cultured in vitro separately and in co-culture to test difference in 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) action on particular cell types. METHODS: The accumulation of TCDD in follicular wall was analysed using coupled capillary gas chromatography mass spectrometry. Whole preovulatory follicles were isolated from ovary and incubated with prolonged exposure to 0.1 nM TCDD or single exposure to 10 nM TCDD for four days. In the second part of experiments direct effects of TCDD on steroidogenesis were investigated in porcine theca cells (Tc) and granulosa cells (Gc) cultured alone and in co-culture (GT). The media were collected after four days for steroid analysis. RESULTS: 59.3% and 81.2% of TCDD added to the culture medium was accumulated after 0.1 and 10 nM, respectively. TCDD in a dose-dependent manner increased estradiol secretion with concomitant progesterone secretion by theca interna cells. On the other hand decrease of both progesterone and estradiol secretion by granulosa cells cultured alone and in co-culture with theca cells was noted. CONCLUSION: Different cell-specific estrogenic or antiestrogenic effect of TCDD were found in ovarian follicles.     

Catalytic destruction of 1,2-dichlorobenzene on V2O5-WO3/Al2O3-TiO2 catalyst

Studies on the catalytic destruction of 1,2-dichlorobenzene were carried out on a specially constructed semi-technical equipment whose most important element was a catalytic reactor with a monolithic catalyst in the form of 150 x 150 x 100 mm cubes. A catalyst made from cordierite with an active layer composed of Al2O3 - 64 wt%, TiO2 - 26 wt%, V2O5 - 6.6 wt% and WO3 - 3.4 wt% was used. The reactor made it possible to carry out the process in the temperature range 150-350 degrees C, at variable catalyst loading and different velocities of gas flow through the reactor. The content of 1,2-dichlorobenzene in the air was analysed by a chromatographic method. A significant effect of catalyst loading and temperature on 1,2-dichlorobenzene destruction efficiency was observed and no effect of the linear flow velocity through the catalyst on o-dichlorobenzene destruction efficiency was reported. The applied vanadium-tungsten catalyst on a monolithic carrier made from TiO2/gamma-Al2O3 revealed very good activity that resulted in an over 80% efficiency of 1,2-dichlorobenzene destruction at the temperature around 250 degrees C at a very high catalyst loading reaching ca. 8200 h(-1). Additionally, in this study the kinetics of 1,2-dichlorobenzene decomposition was determined, specifying the order of reaction and dependence of the decomposition rate constant on temperature, using a simple power-rate law model.     

Study on the determination of PCDDs/Fs and HCB in exhaust gas

The subject of this study was to develop a method of simultaneous determination of PCDDs/PCDFs and HCB in exhaust gases from industrial installations. Sampling to determine PCDDs/PCDFs was conducted using the method described in PN-EN 1948-1: 2006, where the sorption material is polyurethane foam (PUF). In order to simultaneously collect PCDDs/PCDFs and HCB and to avoid sorbent bed breakthrough, it was necessary to apply an additional polyurethane sorption layer. Twenty-seven samples of exhaust gases from various cement plants and 40 samples of exhaust gases from hospital and industrial waste incineration plants collected in 2009/2010 in the entire territory of Poland were examined. The average content of PCDDs/Fs in samples from cement plants amounted to 0.076 ng I-TEQ N m(-3) (range of 0.002-0.62 ng I-TEQ N m(-3)), while the average content of HCB amounted to 10 ng N m(-3) (range of 0.98-60.5 ng N m(-3)). In the case of samples collected from waste incineration plants, the average concentration of PCDDs/Fs was 0.39 ng I-TEQN m(-3) (range of 0.002-5.68 ng I-TEQ N m(-3)). In the case of HCB, the average concentration was 238 ng N m(-3) (range of 3.21-2500 ng N m(-3)). Also, the interdependence of the concentration of PCDDs/PCDFs and HCB was determined in the analysed samples, with the ranges of low and high content of PCDDs/PCDFs being examined separately. In all cases, the determined values of the r correlation coefficient were within the range of 0.7-1.0, which indicates a good correlation between the concentrations of PCDDs/PCDFs and HCB.     

Origin of 2-ethylhexanol as a VOC

2-Ethylhexanol has been identified as a volatile organic compound (VOC) that contributes to the deterioration of indoor air quality. Plasticizers are common components of dust and building materials and are shown to be degraded by a variety of bacteria and fungi to produce 2-ethylhexanol and other metabolites. Of these, the 2-ethylhexanol has significant volatility and was observed in appreciable quantities. The degree to which 2-ethylhexanol is observed as a VOC in air samples would be limited by the fact that many of the microorganisms that are capable of producing this compound are also able to oxidize it to 2-ethylhexanoic acid, which is much less volatile. It is argued that an abiotic degradation mechanism of plasticizers that results in the generation of 2-ethylhexanol is unlikely and, if this did occur, other metabolites should have been observed. Thus, the microbial degradation of plasticizers is the most likely source of 2-ethylhexanol in indoor air.