Biphenyls In Transformer Oil Research Articles

Base-catalysed decomposition of polychlorinated biphenyls in transformer oils by mixture of sodium hydroxide, glycerol and iron.

In this research, a method based on base-catalysed decomposition (BCD) was developed using sodium hydroxide and glycerol for dechlorination of transformer oils with low levels of polychlorinated biphenyls (PCBs). PCB removal and dechlorination efficiencies were measured by gas chromatography and the silver nitrate titration method, respectively. PCB dechlorination and removal efficiencies after 4 h at 250°C and in the presence of iron were 97.4% and 99.8%, respectively. However, in the absence of iron the same efficiencies were calculated to be 79.4 and 99.7%, respectively. The dielectric loss factor of oil refined at 250°C was 0.0064 and did not meet the required standards to be reused in the transformers. However, that refined at 200°C satisfied the standards with acceptable conversion rates. Use of iron, besides increasing conversion rates, changed the mechanism of the reaction from nucleophilic substitution to a combination of hydrodechlorination and nucleophilic substitution. In the presence of iron, highly chlorinated PCBs were converted to less chlorinated PCBs, and this caused the concentration of less chlorinated PCBs to reach a peak and then decline thereafter. The production of PCB 36 confirmed this. However, in the absence of iron particles, all changes in the PCB concentration curves were downward.

Detection of polychlorinated biphenyls in transformer oils in Vietnam by multiphoton ionization mass spectrometry using a far-ultraviolet femtosecond laser as an ionization source

Polychlorinated biphenyls (PCBs) in transformer and food oils were measured using gas chromatography combined with multiphoton ionization mass spectroscopy. An ultrashort laser pulse emitting in the far-ultraviolet region was utilized for efficient ionization of the analytes. Numerous signal peaks were clearly observed for a standard sample mixture of PCBs when the third and fourth harmonic emissions (267 and 200nm) of a femtosecond Ti:sapphire laser (800nm) were employed. The signal intensities were found to be greater when measured at 200nm compared with those measured at 267nm, providing lower detection limits especially for highly chlorinated PCBs at shorter wavelengths. After simple pretreatment using disposable columns, PCB congeners were measured and found to be present in the transformer oils used in Vietnam.

Comparison of solvent extraction and solid-phase extraction for the determination of polychlorinated biphenyls in transformer oil

Solid-phase extraction (SPE) of nine polychlorinated biphenyls (PCBs) from transformer oil samples was evaluated using octadecyl (CI8)-bonded porous silica. The efficiency of SPE of these PCBs was compared with those obtained by solvent extraction with DMSO and hexane. Average recoveries exceeding 95% for these PCBs were obtained via the SPE method using small cartridges containing 100mg of 40pm CI8-bonded porous silica. The average recovery by solvent extraction with DMSO and hexane exceeded 83%. It was concluded that the recoveries and precision for the solvent extraction of PCBs were poorer than those for the SPE.

Analysis of polychlorinated biphenyls in transformer oils by automated on-line coupling reversed phase liquid chromatography-gas chromatography using the through oven transfer adsorption desorption (TOTAD) Interface

An automated method for the direct analysis of polychlorinated biphenyls (PCBs) in transformer oil is presented. The proposed method uses the TOTAD (through oven transfer adsorption desorption) interface for the on-line coupling of reversed phase liquid chromatography and gas chromatography (RPLC-GC). In this fully automated system, the oil is injected directly with no sample pre-treatment step other than dilution with n-propanol and filtration. In the LC step, PCBs are separated from other components of the oils using methanol/water (90:10 v/v) as mobile phase, at a flow rate of 1 mL min−1. The LC fraction containing the PCBs is automatically transferred to the GC by the TOTAD interface and GC analysis enables the separation of the PCB congeners. The proposed method is compared with two other methods: the European Norm (UNE-EN-61619) and that of the American Society for Testing and Materials (ASTM) (D4059-00). The proposed method practically eliminates the time-consuming sample preparation step and avoids errors caused by sample manipulation. The total PCB concentrations obtained with the three methods are similar.

Pretreatment Method for Immunoassay of Polychlorinated Biphenyls in Transformer Oil Using Multilayer Capillary Column and Microfluidic Liquid-Liquid Partitioning

Polychlorinated biphenyls (PCBs) are persistent organic pollutants that are present in the insulating oil inside a large number of transformers. To aid in eliminating PCB-contaminated transformers, PCBs in oil need to be measured using a rapid and cost-effective analytical method. We previously reported a pretreatment method for the immunoassay of PCBs in oil using a large-scale multilayer column and a microchip with multiple microrecesses, which permitted concentrated solvent extraction. In this paper, we report on a more rapid and facile pretreatment method, without an evaporation process, by improving the column and the microchip. In a miniaturized column, the decomposition and separation of oil were completed in 2 min. PCBs can be eluted from the capillary column at concentrations seven-times higher than those from the previous column. The total volume of the microrecesses was increased by improving the microrecess structure, the enabling extraction of four-times the amount of PCBs achieved with the previous system. By interfacing the capillary column with the improved microchip, PCBs in the eluate from the column were extracted into dimethyl sulfoxide in microrecesses with high enrichment and without the need for evaporation. Pretreatment was completed within 20 min. The pretreated oil was analyzed using a flow-based kinetic exclusion immunoassay. The limit of detection of PCBs in oil was 0.15 mg kg(-1), which satisfies the criterion set in Japan of 0.5 mg kg(-1).

Dechlorination of polychlorinated biphenyls in transformer oil using UV and visible light

A study on dechlorination of PCB138 in transformer oil (TO) and 2-propanol (IPA) using 254 nm ultraviolet (UV) light as well as dye sensitized visible light has been conducted. Studies on dechlorination of polychlorinated biphenyls (PCBs) in TO using visible light in the presence of methylene blue (MB) and triethylamine (TEA) (providing a ‘photocatalytic’ cycle) in both deaerated and aerated conditions have been conducted to determine effects of TO, MB and TEA on reaction rates. The results show that photolytic methods are effective in treating PCBs in TO, and that the oil plays a limited adverse role. Under UV irradiation, PCB 138 can be >99% dechlorinated in the presence 0.06% (w/w) TO in IPA within 1 h with a rate constant of 0.0853 min−1, while 47% of PCB138 can be dechlorinated in 92.1% (w/w) TO in IPA within 2 h with a rate constant of 0.0051 min−1. In the ‘photocatalytic’ system, 94% reduction of PCB 138 was achieved within 30 min with a rate constant of 0.0968 min−1 when the solvent was 60.70% (w/w) TO in IPA, while 71% dechlorination of PCB138 was achieved within 30 min with a rate constant of 0.0382 min−1 when 81.62% (w/w) TO was present. In treatment of 30–73 ppm PCBs in TO, the optimal concentration of MB and TEA were found to be 0.5 g/L and 58.08 g/L respectively. Because of quenching by oxygen, deaeration of the solution is necessary for an efficient reaction. The photocatalytic system is especially adapted for treating lower concentration of PCBs in TO.

Analysis of Polychlorinated Biphenyls in Transformer Oil by Using Liquid–Liquid Partitioning in a Microfluidic Device

Polychlorinated biphenyls (PCBs) that are present in transformer oil are a common global problem because of their toxicity and environmental persistence. The development of a rapid, low-cost method for measurement of PCBs in oil has been a matter of priority because of the large number of PCB-contaminated transformers still in service. Although one of the rapid, low-cost methods involves an immunoassay, which uses multilayer column separation, hexane evaporation, dimethyl sulfoxide (DMSO) partitioning, antigen-antibody reaction, and a measurement system, there is a demand for more cost-effective and simpler procedures. In this paper, we report a DMSO partitioning method that utilizes a microfluidic device with microrecesses along the microchannel. In this method, PCBs are extracted and enriched into the DMSO confined in the microrecesses under the oil flow condition. The enrichment factor was estimated to be 2.69, which agreed well with the anticipated value. The half-maximal inhibitory concentration of PCBs in oil was found to be 0.38 mg/kg, which satisfies the much stricter criterion of 0.5 mg/kg in Japan. The developed method can realize the pretreatment of oil without the use of centrifugation for phase separation. Furthermore, the amount of expensive reagents required can be reduced considerably. Therefore, our method can serve as a powerful tool for achieving a simpler, low-cost procedure and an on-site analysis system.

Determination of polychlorinated biphenyls in transformer oil using various adsorbents for solid phase extraction

Various adsorbents for a solid phase extraction (SPE) method were used to study their ability to separate PCBs from transformer oil to rapidly determine their sub-ppm concentration in the transformer oil. Approximately 90% of the transformer oil could be removed from the PCBs by using a hydrophilic–lipophilic balanced copolymer (HLB) adsorbent, but the recovery of deca-chlorobiphenyl (deca-CB) used as a surrogate was only 24.5% due to lose during this cleanup process. The use of a silica adsorbent gave good results with 89.9% recovery of the deca-CB. The recovery of Aroclor 1242 and 1260 were 95.4 and 90.3% on silica, and 98.9 and 83.5% on HLB, respectively. Acid treatment was an essential step in removing the ambiguous interference peaks to help identify the PCBs. A decreased sensitivity of the electron capture detection (ECD) for PCBs was observed due to the presence of the remaining trace oil after the workup procedure. This loss in sensitivity was allowed for by using tetrachloroxylene as an internal standard, and this was found to be reliable for the criteria of quality control by employing an experiment in which LCS was spiked with 2 mg/l of Aroclor 1260 and analyzed each day over a 25 day period. The MDL for the analytical method established in this study is 0.05 mg/l.

Screening method for rapid determination of polychlorinated biphenyls in transformer oil by liquid-liquid extraction and gas chromatography-mass spectrometry

A rapid and simple method was developed for screening polychlorinated biphenyls in transformer oil. The method is based on liquid-liquid extraction in methanol and subsequent direct gas chromatography-mass spectrometric determination. The extent of methanol polarity allows to extract the PCBs, co-extracting a minimum amount of the apolar oil components, thus avoiding the time-consuming steps involving in sample preparation. Since the regulation established internationally for wastes containing PCBs is 50 mg kg-1, the method rapidly determines whether the transformer oil is PCBs-contaminated or not. In order to reach the best conditions for extraction a multivariate optimization was carried out considering two significant variables: volume of methanol and extraction time. Under optimum conditions, recoveries of Aroclor 1256 and Aroclor 1260 were between 80 and 100%, and precision, expressed as relative standard deviation, was from 2 to 4%. The method was applied to real samples polluted with PCBs.

Immunoassay Screening Method for Polychlorinated Biphenyls in Transformer Oil

We described here the results of measuring the PCB levels in eleven hundred transformer oil samples using an immunoassay screening method. Five hundred samples out of the total were remeasured using a GPC/GC/ECD method. A comparison of these results on ROC (receiver operating characteristic) plots showed that the immunoassay provides a useful screening method. In the case that the regulatory concentration of the total PCB was set at 0.5 mg/kg, the most suitable cutoff concentration for the immunoassay for screening was calculated to be at 0.4 mg/kg with false negative and false positive rates of zero and seven percent, respectively.

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlorination of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl 4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc) 2 + i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls.

Effect of photosensitizer diethylamine on the photodegradation of polychlorinated biphenyls

The objective of this study was to investigate the effect of diethylamine and xenon simulated sunlight on the photodegradation of two forms of PCBs including PCBs in transformer oil and PCB congener 138. The result of GC chromatograms illustrated the shifting pattern of higher chlorinated biphenyls in transformer oil degraded to lower chlorinated biphenyls with the extension of exposure time. The effect of diethylamine and xenon simulated sunlight was significant on the photodegradation of both PCBs in transformer oil and congener 138. The initial degradation rates of congener 138 (1.14 × 10 −9 to 4.47 × 10 −9 mol l −1 h −1) were in direct proportion to the initial concentrations of congener 138 which confirmed the pseudo-first-order reaction of PCB photodegradation. The apparent quantum yields ( φ) of congener 138 using diethylamine in xenon photoreactor were ranged between 2.08 × 10 −2 and 9.8 × 10 −4. PCB congeners 123, 97, 70, 67, 33, 29, 17, 12, and 9 were detected as the descendants of the photodegradation of congener 138 through dechlorination. The major pathway of congener 138 photodegradation in this study was via para-dechlorination.

Radiolytic dechlorination of polychlorinated biphenyls in transformer oil and in marine sediment

Radiolytic dechlorination of polychlorinated biphenyls (PCBs) in transformer oil and in marine sediments has been studied. At low PCB concentrations, complete degradation of the PCBs in transformer oil was achieved without degradation of the oil. Addition of an organic base, triethylamine, enhances the radiolytic dechlorination yield. The mechanism of dechlorination has been shown to involve electron transfer to PCBs from various aromatic radical anions formed in the irradiated oil. At high PCB concentrations, large amounts of triethylamine were necessary to achieve complete radiolytic dechlorination. Preliminary results on PCB-contaminated marine sediments demonstrate that addition of 2-propanol to the sediment/water slurry increases the effectiveness of the electron beam treatment.

Optimization of ion trap parameters for the analysis of dilute samples in the presence of an interfering matrix: Analysis of polychlorinated biphenyls in transformer oil

The analysis of dilute samples in the presence of an interfering matrix was improved by optimizing the operating parameters of an ion trap in a GC-ion trap system. For a mixture of nine polychlorinated biphenyls (PCBs) in 1% transformer oil, two strategies were successfully employed to increase signal-to-noise ( S/N) ratios. By limiting the mass range scanned to those m/z values that include most of the ion fragments due to PCBs and increasing the number of microscans per scan in this regime, S/N values were increased by a factor of 1.5. Further improvements in S/N by up to a factor of ten are achieved by raising the radio frequency (rf) storage level so that low molecular weight ions due to the transformer oil are not stored. An upper limit on how high the rf storage level can be adjusted is determined by the storage efficiency of the ion trap which decreases at high rf storage levels. Ion dissociation is also a limiting factor at high rf storage levels. Best detection limits for five of the nine PCBs studied were obtained when the rf storage level was tuned to m/z = 74, a regime where most of the transformer oil ions are no longer stored.

Determination of polychlorinated biphenyls by neutron activation and gamma ray spectrometry

A new method for the determination of polychlorinated biphenyls in transformer oils has been developed. It is based on neutron activation of chlorine in a nuclear reactor and its determination by gamma ray spectrometry. Any organic chlorides present must be purged by volatilization. The method has been tested by analyzing 38 samples of transformer oil by gas chromatography and by this technique. Each time the concentration of chlorine was higher than 38 ppm, the oil was found to be contaiminated by the PCBs. This method provides a fast and cost effective analysis of transformer oils.

Comparison of methods of analysis of polychlorinated biphenyls in oils

In order to standardize and validate methods for the analysis of polychlorinated biphenyls in transformer oil, waste oil, hydraulic fluid and capacitor oil in the concentration range 30–500 ppm, a study was performed which included the variables of capillary/packed column separation, Hall conductivity/electron capture detection and autoquant/area/height peak quantification. Statistical analysis of the results shows that there is no significant overall advantage in any combination of these procedures. In addition, certain statistically significant factors specific to a given oil/analysis method combination have been identified.

Determination of polychlorinated biphenyls in transformer oils by capillary gas chromatography

Determination of polychlorinated biphenyls in transformer oils by capillary gas chromatography

Gas chromatographic method for the analysis of polychlorinated biphenyls in transformer oil

Gas chromatographic method for the analysis of polychlorinated biphenyls in transformer oil