Analysis of polychlorobiphenyls from used transformers for polychlorodibenzofurans

The results of analyses for polychlorodibenzofuran (PCDF) content in two samples of polychlorobiphenyl (PCB) from used electrical transformers are presented and discussed. In neither sample was there evidence for enhanced PCDF concentrations even though one of them had been subjected to overheating while in service.     

Determination of PCBs, PCDDs and PCDFs in insulating oil samples from stored Chinese electrical capacitors by HRGC/HRMS

Homologue and congener profiles of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in commercial PCBs formulations are key information for the source identification of PCBs contamination as well as for the risk assessment caused by potential exposure. The isotope dilution technology in combination with high resolution gas chromatography-high resolution mass spectrometry (HRGC/HRMS) has made the accurate determination of such profiles possible. So far, various commercial PCB formulations except Chinese products have been successfully determined. Two PCBs containing insulating oil samples from stored Chinese electrical capacitors have been determined with the same methodology for comparability. The total concentration PCBs in two oil samples were 790 000 μg g⁻¹ and 720 000 μg g⁻¹, respectively. TriCBs, TetraCBs, and DiCBs were found to be most abundant. Concentration of dioxins contamination in two samples is 650-670 ngTEQ g⁻¹, of which 69-71 ngTEQ g⁻¹ from PCDD/Fs with the predominant congeners of 1,2,7,8-TeCDF; 2,3,7,8-TeCDF; 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDF. The contributions of DL-PCBs in total TEQ in both samples were more than 85%. The dioxin-like toxicity in insulating oils contained in electrical capacitors could be considered receive attention as an important dioxins source if such wastes are not managed in an environmentally sound manner.     

Determination of total organic chlorine and bromine in water samples by adsorption onto activated carbon and neutron activation analysis

A method was developed for the analysis of total organic chlorine and bromine compounds (TOCl, TOBr) in water samples. The method is based on the adsorption of organic compounds on specially prepared activated carbon. Neutron activation analysis (neutron flux 4·10¹² n cm⁻² s⁻¹) was used for the quantitative determination of chlorine and bromine.The factors investigated were the adsorption of organic chlorine and bromine compounds on activated carbon, the effect of pH on the adsorption, the removal of chlorine ions from activated carbon by nitrate washing, the amount of activated carbon required, the adsorption time, the potential number of successive adsorptions and the preservation of samples.The detection limits for TOC1 and TOBr were 5 and 0.5 μg 1⁻¹, respectively, when the sample size was 100 ml.     

Comparison between the accumulation capacity of four lichen species transplanted to a urban site

The capacity to accumulate trace elements from the atmosphere of the lichens Hypogymnia physodes, Parmelia sulcata, Pseudevernia furfuracea and Usnea gr. hirta transplanted to an urban site of N Italy was compared. Twenty-nine elements (Al, As, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hg, I, K, La, Mg, Mn, Ni, Pb, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Zn) were analyzed by Instrumental Neutron Activation Analysis (INAA) and Electro-Thermal Atomic Absorption Spectroscopy (ET-AAS). The ratio between the concentrations of each element in exposed samples to that of control samples (exposed-to-control ratio and EC ratio) was used to investigate the accumulation rates of lichen thalli. The results showed that in general elements did not exhibit well defined trends, but rather showed fluctuations, and indicated that H. physodes, P. furfuracea and U. gr. hirta have a similar accumulation capacity, while that of P. sulcata is lower.     

Polychlorinated biphenyls in surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in East China Sea

The spatial distribution and source of polychlorinated biphenyls (PCBs) in 30 surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in Eastern China were analysed. Total concentrations of PCBs ranged from 9.33 to 19.60 ng g⁻¹ dry weight for all the sampling stations. The observed PCB levels were lower than those in areas of high urbanisation or contamination in the bay. Low-chlorinated PCBs, dominated by tri-PCB, were identified as the prevalent contaminate of surface sediments, and the top three PCB congeners were lighter chlorinated congeners (PCB 8, PCB 18 and PCB 28). These results were in agreement with the fact that tri-PCB compounds are the dominant contaminants in China. The result of the principal component analysis revealed that all samples were similar in composition to Aroclor 1242, suggesting they might originate from electrical capacitors and transformers. The levels of PCBs were significantly correlated with the total organic carbon in the sediments.     

Removal and formation of chlorinated triclosan derivatives in wastewater treatment plants using chlorine and UV disinfection

Triclosan, a common antimicrobial agent, may react during the disinfection of wastewater with free chlorine to form three chlorinated triclosan derivatives (CTDs). This is of concern because the CTDs may be photochemically transformed to tri- and tetra-chlorinated dibenzo-p-dioxins when discharged into natural waters. In this study, wastewater influent, secondary (pre-disinfection) effluent, and final (post-disinfection) effluent samples were collected on two occasions each from two activated sludge wastewater treatment plants, one using chlorine disinfection and one using UV disinfection. Concentrations of triclosan and three CTDs were determined using ultra performance liquid chromatography-triple quadrupole mass spectrometry with isotope dilution methodology. Triclosan and the CTDs were detected in every influent sample at levels ranging from 453 to 4530 and 2 to 98 ng L⁻¹, respectively, though both were efficiently removed from the liquid phase during activated sludge treatment. Triclosan concentrations in the pre-disinfection effluent ranged from 36 to 212 ng L⁻¹, while CTD concentrations were below the limit of quantification (1 ng L⁻¹) for most samples. In the treatment plant that used chlorine disinfection, triclosan concentrations decreased while CTDs were formed during chlorination, as evidenced by CTD levels as high as 22 ng L⁻¹ in the final effluent. No CTDs were detected in the final effluent of the treatment plant that used UV disinfection. The total CTD concentration in the final effluent of the chlorinating treatment plant reached nearly one third of the triclosan concentration, demonstrating that the chlorine disinfection step played a substantial role in the fate of triclosan in this system.     

Atmospheric dispersion of pollutants in Sado estuary (Portugal) using biomonitors

Epiphytic lichen transplants and aerosol samplers were put together in the Setubal area, Portugal. They were analysed by Instrumental Neutron Activation Analysis (INAA) and Proton Induced X-ray Emission (PIXE). The lichen dataset pointed out nine factors. No relevant differentiation was found towards different positioning of the lichens. T-transplants were delayed towards F-transplants, and for both after 3 and 6 months the accumulation was as much as at 9th month. Direct rainfall protection favoured accumulation for a few elements only. The elemental accumulation in lichens depended more on temperature and humidity conditions. Aerosol data towards lichen database showed an excellent correlation.     

Instrumental neutron activation analysis of ambient air dust particulates from metropolitan cities in India

Ambient air dust samples were collected from industrial, commercial and residential areas of four metropolitan cities (Delhi, Calcutta, Madras and Cochin) in India, and were analysed for 27 elements (As, Ba, Br, Ce, Co, Cr, Cs, Cu, Eu, Hf, Hg, Fe, Ga, La, Lu, Na, P, Sb, Sc, Se, Sr, Ta, Tb, Th, Rb, Yb and Zn) by Instrumental Neutron Activation Analysis (INAA). Samples were irradiated with thermal neutrons in a nuclear reactor for 1 day and counted by high resolution gamma spectrometry at different intervals. Several environmental standards such as Coal (SRM 1932b); Urban Particulate Matter (SRM 1648) from NIST, USA; Vehicle Exhaust from NIES, Japan; and Soil-5 from IAEA, Vienna were also analysed for quality assurance. The results reveal that the concentrations of several pollutant elements in dust samples from the four cities are highly variable. Wide differences were observed for elemental concentrations of As, Ba, Br, Cu, Cr, Hg, Fe, Sb, Se and Zn and these variations are explained in terms of their possible sources of origin.     

A rapid method for determination of Aroclor 1260 in cattle adipose tissue

Abstract

A simple analytical procedure for the determination of Aroclor 1260 in cattle adipose tissue is described. The polychlorinated biphenyls residues are extracted from the tissue using a soxhlet extractor and the extracts are cleaned up using a florisil SEP‐PAK cartridge. The residues are detected using a gas chromatograph equipped with an electron capture detector. The effect of extraction time of the Aroclor 1260 residues from the tissue has been investigated and a period of four hours is found to give satisfactory percent recoveries. Greater than 85 percent recoveries were obtained from adipose tissue spiked with Aroclor 1260. The method can be used to detect Aroclor 1260 residue levels as low as 0.10 parts per million.

The method was used to analyze thirty‐one cattle adipose tissue samples out of which twenty‐six samples were taken from cattle suspected of exposure to a pasture containing electrical transformers and capacitors containing Aroclor 1260. Five control samples were collected from cattle with no known exposure. All twenty‐six samples were found to contain non‐detectable Aroclor 1260 residues.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

Presence of Aeromonas spp in water from drinking-water- and wastewater-treatment plants in Mexico City.

The frequency of Aeromonas spp in three wastewater-treatment plants (WWTPs) and two drinking-water plants (DWPs) in México City was determined. Samples were taken throughout a year by the Moore's swab technique. A total of 144 samples were obtained from WWTPs and 96 from DWPs of both incoming and outflowing water. Aeromonas spp was isolated in 31% of the samples, from both kinds of sources. The technique used for the isolation of the pathogen was suitable for samples with high associate microbiota content and for those with a scarce microbial content. The presence of mesophilic-aerobic, coliform, and fecal-coliform organisms was investigated to determine whether there was any correlation with the presence of Aeromonas spp. Most samples from WWTP, which did not comply with the Mexican standards, had the pathogen, and some of the samples from the outflow of the DWP, which were within the limits set by the Mexican standards, also had Aeromonas spp. Most samples containing Aeromonas spp. had concentrations below 0.1 ppm residual chlorine, and the strains were resistant to 0.3 ppm, which supports the recommendation to increase the residual chlorine concentration to 0.5 to 1.0 ppm, as recommended by the Mexican standards.     

Diastereoisomer- and enantiomer-specific determination of hexabromocyclododecane in fish oil for food and feed

Fish oils are one of the main sources of ω-3 fatty acids. However, they can present elevated levels of some lipophilic pollutants, such as hexabromocyclododecanes (HBCDs). Since data about HBCDs in fish oil samples are very limited, in this study, 25 samples of fish oil for feed and food have been analyzed. Total HBCDs, as well as, α-, β- and γ-diastereoisomers have been determined. Total HBCDs ranged from 0.09 to 26.8 ng g⁻¹, with higher concentrations in fish oil for feed (average value of 9.69 ng g⁻¹) than those for food (1.14 ng g⁻¹). Concentrations of α-HBCD (average value of 4.12 ng g⁻¹ in feed samples and 0.48 ng g⁻¹ in food samples) and γ-HBCD (5.05 and 0.43 ng g⁻¹ respectively) were higher than that of β-HBCD (0.52 and 0.19 ng g⁻¹ respectively) in most of the samples. However, none of them was predominant in the samples. Concentrations of HBCDs were compared to concentrations of other pollutants and correlation between dioxin and dioxin-like PCBs levels and HBCDs levels were observed. Intake of HBCDs was calculated for fish oil with human consumption purposes and it ranged from 0.08 to 5.38 ng HBCDs d⁻¹, which could contribute significantly to HBCDs total intake. Enantiomeric fractions were also determined. No clear enrichment was observed for γ-HBCD, while (−)-α-HBCD enrichment was detected in some samples.     

Effects of regional differences in waste composition on the thermal formation of polychlorinated aromatics during incineration

Two artificial wastes (A and B) whose contents reflect regional differences in municipal solid waste composition, were used to investigate the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) during incineration. Flue gas samples were simultaneously collected at three ports in the post-combustion zone corresponding to flue gas temperatures of 400, 300, and 200 °C. The combustion of Waste B, which had a higher chlorine and metal content than Waste A, produced greater levels of highly-chlorinated homologues, as demonstrated by a higher degree of chlorination. The total concentrations of PCDDs, PCDFs, PCBs, and PCNs formed in the combustion of both wastes increased as temperature decreased along the convector. There were no significant differences in total concentrations between Waste A and Waste B combustion at specific temperatures, with exception of PCDFs at 400 °C. Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) modeling, used to evaluate the data for all compound groups, suggest that during flue gas quenching at temperatures of 400 °C low-chlorinated homologues are preferentially formed in the presence of copper, which is known to be a very active catalyst for this process. At 300 and 200 °C, the formation of highly-chlorinated homologues is favored.     

Some technical issues in managing PCBs

Polychlorinated biphenyls (PCBs) were important industrial chemicals featuring high thermal and chemical stability and low flammability. They were widely used as dielectric and thermal fluid in closed electro-technical applications (transformers, capacitors…) and also in numerous dispersive uses, ranking from auto-copying paper to sealant or coatings. During the 1960s, severe environmental consequences started becoming apparent. The stability of PCBs contributed to their persistence in the environment, their lipophilic character to bio-magnification. Fish-eating species seemed threatened in their existence. In Japan and in Taiwan, thousands of people consumed PCB-contaminated oil. The production of PCBs stopped completely during the 1980s. Usage could continue in closed applications only. In this paper, particular attention is given to two issues: the cleaning of PCB electric transformers and the potential impact of PCB-containing building materials. Other contributions will cover the management and treatment of PCB-contaminated soil, sludge or fly ash. The complete survey is being prepared by request of the Knowledge Center for Engineers and Professionals.     

Determination of endosulfan residues in eggplant (Solanum melongena) by ELISA

Eggplant samples were analyzed for endosulfan residues using ELISA, a technique recognized as a promising tool for screening environmental contaminants. Calibration curve for endosulfan was standardized using kits developed by CFTRI Mysore. Farm gate samples of eggplant from 12 different locations were analyzed. The matrix effect was removed by charcoal clean-up. The results were compared with gas chromatographic (GC) analysis. The residues in different samples were in the range of 5-226 ppb. Correlation coefficient between the two methods was found to be 0.98.     

Loss of particulate contaminants from plant canopies under wet and dry conditions

There is a requirement for data describing the loss with time of particulate contamination from plant canopies. Measurements were made of the loss rates of monodispersed silica spheres (three sizes, with Mass Median Aerodynamic Diameters (MMADs) 1.9, 5.3 and 8.4 microm) from wheat (Triticum aestivum) and broad bean (Vicia faba) canopies. The spheres were labelled with tracers detectable by Instrumental Neutron Activation Analysis (INAA). Canopies were contaminated under realistic turbulence conditions in a wind tunnel, then removed to sheltered and exposed field sites or to a glasshouse containing a rain simulator. Samples were taken periodically, and the level of contamination per plant determined by INAA. Statistical analysis of the resulting data suggested an offset exponential loss model, with a residue of deposit that is not lost over time. Loss half-lives in the order of 1-2 days were obtained for an exposed wheat crop and 3-4 days for a partially sheltered wheat crop, with permanent residues of initial deposit for the exposed crop of 4-8%, and for the partially sheltered crop of 22-52%. A broad bean crop under glasshouse conditions showed loss half-lives of 0.5-1.5 days with residues of 22-26% initial contamination. A double exponential loss model also fitted the data well in some cases, and it is possible that a slow loss of the residual deposit occurs, being masked by noise in the current data set.     

Atmospheric trace element concentrations in total suspended particles near Paris,France

To evaluate today’s trace element atmospheric concentrations in large urban areas, an atmospheric survey was carried out for 18 months, from March 2002 to September 2003, in Saclay, nearby Paris. The total suspended particulate matter (TSP) was collected continuously on quartz fibre filters. The TSP contents were determined for 36 elements (including Ag, Bi, Mo and Sb) using two analytical methods: Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The measured concentrations were in agreement within the uncertainties with the certified values for the polycarbonate reference material filter SRM-2783 (National Institute for Standard Technology NIST, USA). The measured concentrations were significantly lower than the recommended atmospheric concentrations. In 2003, the Pb atmospheric level at Saclay was 15 ng/m³, compared to the 500 ng/m³ guideline level and to the 200 ng/m³ observed value in 1994. The typical urban background TSP values of 1–2, 0.2–1, 4–6, 10–30 and 3–5 ng/m³ for As, Co, Cr, Cu and Sb, respectively, were inferred from this study and were compared with the literature data. The typical urban background TSP concentrations could not be realised for Cd, Pb and Zn, since these air concentrations are highly influenced by local features. The Zn concentrations and Zn/Pb ratio observed in Saclay represented a characteristic fingerprint of the exceptionally large extent of zinc-made roofs in Paris and its suburbs. The traffic-related origin of Ba, Cr, Cu, Pb and Sb was demonstrated, while the atmospheric source(s) of Ag was not identified.     

Dioxin formation in pulp and paper mills of India

Samples of effluents, sludge, pulp, final products (paper) and soil were collected from the identified pulp and paper mills in India. The samples were analysed for 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCDD) and other dioxin congeners and precursors. Pulp and paper mills using chlorine for the bleaching process showed the presence of 2,3,7,8-TCDD in effluent samples. In the effluent and pulp samples from mills where chlorine dioxide was used as a bleaching agent, the 2,3,7,8-TCDD congener ranged from below the detection limit 0.05 to 0.12 ngL⁻¹/ngg⁻¹. The relative standard deviation of reproducibility and the percent recovery of 2,3,7,8-TCDD were 2.07 and 82.4% in pulp and 2.8 and 92% in effluent, respectively. The 1,3,6,8-TCDD was the only other major dioxin congener found in the treated and untreated effluent and sludge samples. However, dichlorobenzene, trichlorophenyl, and hexachlorobiphenyl were detected in all samples. The formation of dioxins can be minimised by replacing chlorine with chlorine dioxide in bleaching processes in pulp and paper mills.     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

Determination of indicator polychlorinated biphenyls (PCBs) by gas chromatography–electron capture detector

An effective method for determination of indicator polychlorinated biphenyls (PCBs) has been validated using gas chromatography (GC) equipped with electron capture detector (ECD). The GC–ECD method was validated by determining the linear range (working range) for determination of the compounds, minimum detectable quantities (MDQ), the precision and accuracy of the method for the analysis of the compounds. MDQ obtained for the compounds ranges from 0.0005 to 0.002 ng. Indeed the method was found to be more sensitive as the number of chlorine atoms attached to the biphenyl increases. The precision and accuracy of the GC method validated ranges from 2.4% to 14.5% and −7.0% to 14.6% respectively. Coefficient of variation associated with the repeatability of the retention times and corresponding peak areas was found to be 0.0001–0.0007 for the retention times and 0.0014–0.059 for the peak areas. Percentage recoveries for the compounds were in the range of 95.7–101.0%. The validated method was then applied to determine levels of indicator PCBs in sediments sampled from eleven sampling points along the Lake Bosuntwi in Ghana and the highest PCB load of 19.17 ng g⁻¹ was recorded at Pipie No. 2. PCB 52 and PCB 101 were found to be the most ubiquitous indicator PCBs in the study area, both with 90.91% occurrence.