Adsorption of DDT and PCB by Nanomaterials from Residual Soil.

This paper presents the findings of a study on adsorption of dichlorodiphenythreechloroethen (DDT) and polychlorinated biphenyls (PCBs) on three nanomaterials including Multi walled Carbon Nanotube (MWNT), nano-clay and nano-alumina. DDT and PCBs are of significant concern due their high toxicity and long environmental half-lives. Experiments were conducted using batch adsorption procedures at different DDT and PCBs concentrations, from 10 to 60 mg/L. The amounts of MWNT, nano-clay and Nano-alumina used were 0.25%, 0.50%, 0.75%, 1%, 2% and 10%. The adsorption of PCBs solution onto the MWNT, nano-clay and nano-alumina was characterized by an initial rapid adsorption which eventually became constant within 22, 20, and 17 hours, respectively. The adsorption of DDT solution onto the MWNT, nano-clay and nano-alumina was also characterized by an initial rapid adsorption which gradually became constant within 22, 22 and 16 hours, respectively. Results of this study indicated that MWNT was a better adsorbent material compared to nano-clay and nano-alumina for both contaminants in this study. While at 10% of MWNT 88.9% and 77% of DDT and PCB were removed by MWNT, respectively. The effect of pH and temperature were also investigated.

Application of Kohonen neural network for evaluation of the contamination of Brazilian breast milk with polychlorinated biphenyls.

Due to the tendency of polychlorinated biphenyls (PCB) to accumulate in matrixes with high lipid content, the contamination of the breast milk with these compounds is a serious issue, mainly to the newborn. In this study, milk samples were collected from breastfeeding mothers belonging to 4 Brazilian regions (south, southeast, northeast and north). Twelve PCB were analyzed by HS-SPME-GC-ECD and the corresponding peak areas were correlated to the answers to a questionnaire of general habits, breastfeeding and characteristics of the living places. To realize this exploratory analyze, self-organizing maps generated applying Kohonen neural network were applied. It was possible to verify the occurrence of different PCB congeners in the breast milk relating to the region of the Brazil that the breastfeeding lives, the proximity to an industry, the proximity to a contaminated river or sea, the type of milk (colostrum, foremilk and hindmilk) and the number of past pregnancies.

Validation of one-step cleanup and separation method of polychlorinated biphenyls, organochlorine pesticides, and polycyclic aromatic hydrocarbons from atmospheric gas- and particle-phase samples.

A one-step cleanup method is described for the determination of PAHs, PCBs and OCPs in air (gas and particulate phase) samples. Analytes were extracted from ambient air samples using soxhlet extraction with a solvent mixture of dichloromethane and petroleum ether (1:4) for 24h. They were concentrated, separated and fractionated on a florisil and alumina column. The amounts of florisil (1g or 2g) with/without alumina were tested in the cleanup column. The study systematically investigated the effects of solvent types, and the amounts of florisil and alumina, on the performance of the cleanup process. The first fraction was eluted with 25 mL hexane, and analyzed for PCBs. The second fraction was collected via 40 mL hexane-ethyl acetate (1:1) solvent mixture, and analyzed for OCPs and PAHs. The optimized method yielded average recoveries between 88% and 99% for PCBs; 56% and 118% for PAHs; and 51% and 128% for OCPs. Other validation parameters were also investigated, such as MDL, LOQ, linear range, sensitivity (r(2)). An oven-program optimization and adjustment of GC-MS were performed. For internal quality control, surrogate recoveries and field blanks values were calculated. External calibration curves were prepared for PAHs, and internal calibration curves were preferred for OCP and PCBs.

FITC-modified PPy nanotubes embedded in nanoporous AAO membrane can detect trace PCB20 via fluorescence ratiometric measurement.

A highly sensitive and selective fluorescence ratiometric sensor membrane for 2,3,3'-trichlorobiphenyl has been achieved, via depositing polypyrrole nanotubes (PPyNTs, the fluorescence indicator) in nano-porous anodic aluminium oxide (NPAAO) template and subsequently immobilizing fluorescein isothiocyanate (as an internal reference) onto the inner walls of the PPyNTs embedded in the NPAAO.

Persistent organic pollutants in fish oil supplements on the Canadian market: polychlorinated biphenyls and organochlorine insecticides.

Fish and seal oil dietary supplements, marketed to be rich in omega-3 fatty acids, are frequently consumed by Canadians. Samples of these supplements (n = 30) were collected in Vancouver, Canada, between 2005 and 2007. All oil supplements were analyzed for polychlorinated biphenyls (PCBs) and organochlorine insecticides (OCs) and each sample was found to contain detectable residues. The highest SigmaPCB and SigmaDDT (1,1,1-trichloro-di-(4-chlorophenyl)ethane) concentrations (10400 ng/g and 3310 ng/g, respectively) were found in a shark oil sample while lowest levels were found in supplements prepared using mixed fish oils (anchovy, mackerel, and sardine) (0.711 ng SigmaPCB/g and 0.189 ng SigmaDDT/g). Mean SigmaPCB concentrations in oil supplements were 34.5, 24.2, 25.1, 95.3, 12.0, 5260, 321, and 519 ng/g in unidentified fish, mixed fish containing no salmon, mixed fish with salmon, salmon, vegetable with mixed fish, shark, menhaden (n = 1), and seal (n = 1), respectively. Maximum concentrations of the other OCs were generally observed in the seal oil. The hexachlorinated PCB congeners were the dominant contributors to SigmaPCB levels, while SigmaDDT was the greatest contributor to organochlorine levels. Intake estimates were made using maximum dosages on manufacturers' labels and results varied widely due to the large difference in residue concentrations obtained. Average SigmaPCB and SigmaDDT intakes were calculated to be 736 +/- 2840 ng/d and 304 +/- 948 ng/d, respectively.

Removal of dioxins and dioxin-like PCBs from fish oil by countercurrent supercritical CO2 extraction and activated carbon treatment.

It has been known that fish oils are prone to contamination by polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs). In this study, the removal of contaminants from fish oil by countercurrent supercritical CO(2) extraction (CC-SCE) and activated carbon treatment was investigated. Fish oil was treated by CC-SCE at 70 degrees C and 30MPa and with a CO(2)/oil ratio of 72; this resulted in a 93% reduction in the sum of PCDDs, PCDFs and DL-PCBs concentration level by and 85% reduction in toxic equivalency (TEQ). CC-SCE uses 40% less CO(2) and yields 30% more refined oil than semi-batch-type processes. Subsequent treatment by activated carbon reduced the concentration level by 94% and TEQ by 93%. CC-SCE is effective for the removal of DL-PCBs, whereas activated carbon treatment is effective for the removal of PCDD/Fs. These results reveal that the combination of CC-SCE and activated carbon treatment is applicable to the removal of PCDD/Fs and DL-PCBs from fish oil.

Equilibrium sampling: partitioning of organochlorine compounds from lipids into polydimethylsiloxane.

Polydimethylsiloxane (PDMS) can be used for equilibrium sampling of environmental pollutants in a large variety of matrices including biota. For comparison with lipid-normalized concentrations e.g. from biota monitoring programmes, reliable lipid to PDMS partition ratios (K(Lipid,PDMS)) are required. Additionally, K(Lipid,PDMS) facilitate comparison of equilibrium sampling data obtained in various environmental media and can be helpful to convert equilibrium sampling data into a more informative form. This work investigated the equilibrium partitioning of polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs) between lipids from biota of different trophic levels and PDMS. One vegetable oil, a fish oil and seal oil were investigated. The lipid to PDMS partition ratios were compound-specific and ranged from 14.5 to 62.9 g/g with correction for lipid uptake into the PDMS and from 13.0 to 54.8 g/g without correction. Additionally, PDMS served as a reference partitioning phase for the accurate determination of lipid to lipid partition ratios, which for all analytes were close to unity. Evaluating the results in a bioaccumulation context, they indicate that the equilibrium partitioning of neutral lipophilic environmental contaminants into the lipids of the three investigated species will be very similar, although they represent three distinct trophic levels.

Sustainable decontamination of an actual-site aged PCB-polluted soil through a biosurfactant-based washing followed by a photocatalytic treatment.

A two phases process consisting of a soya lecithin (SL)-based soil washing process followed by the photocatalytic treatment of resulting effluents was developed and applied at the laboratory scale in the remediation of an actual-site soil historically contaminated by 0.65 g/kg of polychlorinated biphenyls (PCBs). Triton X-100 (TX) was employed in the same process as a control surfactant. SL and TX, both applied as 2.25 g/L aqueous solutions, displayed a comparable ability to remove PCBs from the soil. However, SL solution displayed a lower ecotoxicity, a lower ability to mobilize soil constituents and a higher soil detoxification capacity with respect to the TX one. The photocatalytic treatment resulted in marked depletions (from 50% to 70%) of total organic carbon (TOC) and PCBs initially occurring in the SL and TX contaminated effluents. Despite the ability of SL to adversely affect the rate of TOC and PCB photodegradation, higher PCB depletion and dechlorination yields along with lower increases of ecotoxicity were observed in SL-containing effluents with respect to the TX ones at the end of 15 days of treatment. The two phases process developed and tested for the first time in this study seems to have the required features to become, after a proper optimization and scale up, a challenging procedure for the sustainable remediation of actual site, poorly biotreatable PCB-contaminated soils.

Bioactive polychlorinated bibenzyls from the liverwort Riccardia polyclada.

GC-MS and (1)H NMR spectroscopic profiling of a CDCl 3 extract of the liverwort Riccardia polyclada (syn. R. umbrosa) revealed the presence of four main compounds bearing several chlorine atoms on a bibenzyl skeleton. Separation of a CH 2Cl 2 extract was achieved using preparative TLC, and structures 1- 4 were proposed on the basis of spectroscopic evidence. Compounds 1- 4 were active in a brine shrimp lethality bioassay ( Artemia salina). In addition, 2 and 4 displayed moderate antifeedant activity in disk-choice bioassays with Spodoptera littoralis larvae and inhibited the growth of Cladosporium herbarum cultures on TLC plates.

Granular activated carbon adsorption and microwave regeneration for the treatment of 2,4,5-trichlorobiphenyl in simulated soil-washing solution.

The treatment of 2,4,5-trichlorobiphenyl (PCB29) in simulated soil-washing solution by granular activated carbon (GAC) adsorption and microwave (MW) regeneration was investigated in this study. The PCB29 adsorption process was carried out in a continuous flow adsorption column. After adsorption, the PCB29-loaded GAC was dried at 103 degrees C, and regenerated in a quartz reactor by 2450MHz MW irradiation at 700W for 5min. The efficacy of this procedure was analyzed by determining the rates and amounts of PCB29 adsorbed in successive adsorption/MW regeneration cycles. Effects of the regeneration on the textural properties and the PCB29 adsorption capacity of GAC were examined. It was found that after several adsorption/MW regeneration cycles, the adsorption rate of GAC increased, whereas, the adsorption capacity decreased, which could be explained according to the change of textural properties. Most of the PCB29 adsorbed on GAC was degraded within 3min under MW irradiation, and the analysis of degradation products by GC-MS demonstrated that PCB29 experienced dechlorination during this treatment.

Selective pressurized liquid extraction of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls from food and feed samples.

Selective pressurized liquid extraction (PLE) of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) from various food and feed samples was performed with a selective PLE method previously developed for bulk PCBs. The method utilizes sulfuric acid impregnated silica inside the extraction cell to oxidize coextracted fat. Extractions were performed at 100 degrees C with n-heptane for 5 min in two cycles. Data obtained by selective PLE combined with gas chromatography/high-resolution mass spectrometry (GC-HRMS) were compared to concentrations derived from reference laboratories applying conventional sample preparation and GC-HRMS. Experiments performed on spiked vegetable oil, naturally contaminated crude fish oil and oil containing compound feed samples showed good results for these relatively simple matrices. The accuracy was generally +/-20% as compared to spiked levels or to values obtained by the reference laboratories. The precision, measured as the relative standard deviation (RSD) for 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalency values (TEQs), was below 10% in all cases. The method was also tested on naturally contaminated herring tissue, chicken tissue, pork tissue and sepiolitic clay, which all caused some trouble. It was observed that sufficient amounts of sodium sulfate should be used for dehydration of tissue samples and additionally, the cells should not be packed too dense in order to avoid suppressed extraction efficiency. Once this was attended to, satisfactory data could be obtained, except for sepiolithic clay. This study demonstrates that selective PLE can be applied with success to a number of food and feed matrices in analysis of PCDD/Fs and dl-PCBs. Since the fat removal step is on-line, the selective PLE method will reduce time and solvent consumption for sample preparation as compared to traditional clean-up.

Determination of mono- to octachlorobiphenyls in fish oil using florisil adsorption followed by headspace solid-phase microextraction and gas chromatography with time-of-flight mass spectrometric detection.

A simple and reliable method for the determination of polychlorinated biphenyls (PCBs) from mono- to octachlorobiphenyls in fish oil for dietary supplement is described. The method combines Florisil clean up and headspace solid-phase microextraction on 65 microm polydimethylsiloxane-divinylbenzene (PDMS-DVB). Analyte detection was carried out using GC-time-of-flight mass spectrometry (GC-TOF-MS). Fifty three PCB congeners including the seven indicator PCBs (IUPAC Nos. 28, 52, 101, 118, 138, 153 and 180) were analyzed. Under optimal conditions, the method detection limit (MDL) of each congener in the range from 0.8 to 31 ng/g was found. A certified reference material (BCR-349) was analyzed and it showed good agreement with the certified data.

Detailed study on the levels of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil.

One bottle of Yusho rice oil was obtained from a Yusho family in 1998. The levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in the causal oil were investigated with two different approaches and the individual concentrations of all the 17 2,3,7,8-substituted PCDD/F and 14 coplanar PCB (Co-PCB) congeners were elucidated for the first time. The concentrations of PCDDs and PCDFs were found to be 0.60 and 8.8 ppm, respectively. For PCBs, more than 130 PCB peaks were observed and a total concentration of 850 ppm including 170 ppm of Co-PCBs was obtained. The toxic equivalents (TEQs) of PCDDs, PCDFs, and Co-PCBs were calculated to be 17, 470, and 120 ppb, respectively. The relative contribution of these classes to the total TEQ in Yusho oil is 3%, 77%, and 20%, respectively, indicating that PCDFs play a major role in the toxicity of Yusho oil. Furthermore, it was confirmed that 2,3,4,7,8-penta-CDF contributes 58% to the total TEQ, supporting the view that this compound is the principal causal agent in Yusho poisoning. It is noteworthy that the most toxic 2.3,7,8-tetra-CDD was newly discovered, although it contributes only 0.1% to the total TEQ. Based on our data, the smallest TEQ intake during the latent period was estimated to be 0.067 mg for Yusho patients. This value is about 60% of that previously reported, suggesting a lower minimum threshold level for the development of the toxic symptoms of Yusho.

Comparison of fat retainers in accelerated solvent extraction for the selective extraction of PCBs from fat-containing samples.

Five types of fat retainers were investigated for the lipid-free extraction of PCBs from fat-containing matrixes using accelerated solvent extraction: florisil, basic alumina, neutral alumina, acidic alumina, and sulfuric acid-impregnated silica. All of the fat retainers generated fat-free extracts when the fat/fat retainer ratio was 1:40. Sulfuric acid-impregnated silica and florisil were the only retainers that gave completely clear extracts, and the former was the only not to show any reaction when treated with sulfuric acid after the extraction. Using sulfuric acid-impregnated silica as fat retainer, on-line cleanup of fat-containing matrixes was possible, as demonstrated for naturally contaminated fish meal as well as certified cod liver oil (CRM 349).

A new sample preparation technique for organochlorines in cod liver oil combining SPE and NP-HPLC with HRGC-ECD.

The analysis of semivolatile organochlorines (polychlorinated biphenyls and chlorinated pesticides) in less polluted biomaterials requires specific strategies in controlling the blank in sample preparation. The procedure described here allows to decrease significantly the level of contamination during the clean-up step of fish oil. Solid-phase-extraction (SPE) on LiChrolut EN and normal phase HPLC in the normal- and the backflush-mode were used to reduce the amount of solvents needed and the analysis time compared to established clean-up procedures. With a certified reference material (BCR-CRM 349; Cod Liver Oil) the precision and effectiveness of the new method were validated. Recovery rates of the Internal Standards (PCB 103 and TCN) lay between 75% and 90% at the microg/kg lipid level. The quantitative analyses were carried out by high resolution gas chromatography with electron capture detector (HRGC-ECD).

Determination of organochlorine compounds in fatty matrices. Application of rapid off-line normal-phase liquid chromatographic clean-up.

A clean-up method for organochlorine compounds in fatty samples based on normal-phase liquid chromatography (NPLC) is described. To this end, an existing clean-up procedure which uses column switching for the separation of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) from the fat matrix was simplified to a single silica LC column procedure. The use of an LC column packed with 3 microns silica enables complete fat/OCP separation in a total fraction volume of 12 ml, and results in a fully automated clean-up procedure that takes only 32 min per sample. The method showed average recoveries of 80-110% in the concentration range of 1-510 micrograms/kg, with relative standard deviations of less than 10%. Limits of determination were in the range of 0.5-50 micrograms/kg. The simplified approach has shown its potential for a variety of samples, such as milk, pork fat, animal feed and cod liver oil, showing its general applicability to fatty samples.

Supercritical fluid extraction of PCBs from human adipose tissue for HRGC/LRMS analysis.

Supercritical fluid extraction (SFE) of 36 PCBs from human adipose is presented. Selective extraction of the PCBs is achieved using supercritical CO2 with a density of 0.9 g/ml (281 bar) at 40 degrees C and with AlOx as a fat retainer. Compared to the traditional liquid extraction method followed by further sample clean up, SFE is not only faster (2 hours compared to three days) but also utilises lower amounts of organic solvents (4 ml compared to over 500 ml). The recoveries of 7 added 13C labelled PCBs are 83-106%. The repeatability in the analysis of 36 PCBs in 6 identical samples is excellent, with an average R.S.D. of less than 10%.